Process to make non-coordinating anion type activators in aliphatic and alicyclic hydrocarbon solvents

ABSTRACT

The present disclosure provides borate activators comprising cations having linear alkyl groups, catalyst systems comprising, and processes for polymerizing olefins using such activators. Specifically, the present disclosure provides polymerization activator compounds which may be prepared in, and which are soluble in aliphatic hydrocarbon and alicyclic hydrocarbon solvents.

This application claims priority to and the benefit of U.S. Ser. No.62/662,972, filed Apr. 26, 2018 and U.S. Ser. No. 62/769,208, filed Nov.19, 2018.

FIELD

The present disclosure provides group 13 metallate (such as borateactivators), a process for producing borate activators in aliphatic andalicyclic solvents, catalyst systems comprising such activators, andprocesses for polymerizing olefins using such activators.

BACKGROUND

Polyolefins are widely used commercially because of their robustphysical properties. Polyolefins are typically prepared with a catalystthat polymerizes olefin monomers. Therefore, there is interest infinding new catalysts and catalyst systems that provide polymers havingimproved properties.

Catalysts for olefin polymerization are often based on metallocenes ascatalyst precursors, which are activated either with an alumoxane or anactivator containing a non-coordinating anion. A non-coordinating anion,such as tetrakis(pentafluorophenyl)borate, is capable of stabilizing theresulting metal cation of the catalyst. Because such activators arefully ionized and the corresponding anion is highly non-coordinating,such activators can be effective as olefin polymerization catalystactivators. However, because they are ionic salts, such activators areinsoluble in aliphatic hydrocarbons and only sparingly soluble inaromatic hydrocarbons. It is desirable to conduct most polymerizationsof α-olefins in aliphatic hydrocarbon solvents due to the compatibilityof such solvents with the olefin monomer and to reduce the aromatichydrocarbon content of the resulting polymer product. Typically, ionicsalt activators are added to such polymerizations in the form of asolution in an aromatic solvent such as toluene. The use of even a smallquantity of such an aromatic solvent for this purpose is undesirablesince it must be removed in a post-polymerization devolatilization stepand separated from other volatile components, which is a process thatadds significant cost and complexity to any commercial process. Inaddition, the activators often exist in the form of an oily, intractablematerial which is not readily handled and metered or preciselyincorporated into the reaction mixture.

In addition, polymer products, such as isotactic polypropylene, formedusing such activators can have lower molecular weights (e.g., Mw lessthan about 100,000) and a high melt temperature (Tm) (e.g., Tm greaterthan about 110° C.).

U.S. Pat. No. 5,919,983 discloses polymerization of ethylene and octeneusing a catalyst system comprising [(C₁₈)₂MeN)]⁺[B(PhF₅)₄]⁻ activatorhaving four fluoro-phenyl groups bound to the boron atom and two linearC₁₈ groups bound to the nitrogen, as well as describing other lineargroups at column 3, line 51 et seq.

U.S. Pat. No. 8,642,497 discloses the preparation ofN,N-dimethylanilinium tetrakis(heptafluoronaphth-2-yl)borate anion.

US 2003/0013913 (granted as U.S. Pat. No. 7,101,940) discloses variousactivators such asN,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate [0070],and N,N-diethylbenzylammoniumtetrakis(pentafluorophenyl)borate [0124].

US 2002/0062011 discloses phenyl dioctadecylammonium(hydroxyphenyl)tris(pentafluorophenyl) borate at paragraph [0200] and(pentafluorophenyl) dioctadecylammonium tetrakis(pentafluorophenyl)borate at paragraph [0209].

U.S. Pat. Nos. 7,799,879, 7,985,816, 8,580,902, 8,835,587, andWO2010/014344 describe ammonium borate activators that include some thatuse a tetrakis(heptafluoronaphth-2-yl)borate anion.

There is a need for activators that are soluble in aliphatichydrocarbons and capable of producing polyolefins having a highmolecular weight and high melt temperature. Likewise, there is a needfor activators that are soluble in aliphatic hydrocarbons and capable ofproducing polyolefins at high activity levels where the polymerspreferably have high molecular weight and/or high melt temperature.

References of interest include: WO 2002/002577; U.S. Pat. Nos.7,087,602; 8,642,497; 6,121,185; 8,642,497; US2015/0203602; and U.S.Ser. No. 62/662,972 filed Apr. 26, 2018, CAS number 909721-53-5, CASnumber 943521-08-2.

SUMMARY

This invention relates to a process to produce an activator compoundcomprising the steps of contacting a compound according to formula (A)with a compound having the general formula M-(BR⁴R⁵R⁶R⁷) in an aliphatichydrocarbon solvent, an alicyclic hydrocarbon solvent, or a combinationthereof, at a reaction temperature and for a period of time sufficientto produce a mixture comprising the activator compound according toformula (I) and a salt having the formula M(X); wherein formula (A) isrepresented by:

wherein formula (I) is represented by:

wherein in each of formula (A) and (I):each of R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independently a hydrogen ora C₁-C₄₀ linear alkyl; R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² togethercomprise 15 or more carbon atoms; each of R⁴, R⁵, R⁶, and R⁷ comprisesan aromatic hydrocarbon having from 6 to 24 carbon atoms; at least oneof R⁴, R⁵, R⁶, and R⁷ is substituted with one or more fluorine atoms; Xis halogen; and M is a Group 1 metal.

In embodiments, a 1 millimole per liter mixture of the activatorcompound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or acombination thereof, forms a clear homogeneous solution at 25° C.

The present disclosure also relates to a catalyst system comprising anactivator and a catalyst compound.

The present disclosure also relates to a polymerization processcomprising the steps of forming the activator in an aliphatic solvent,combing the activator with a catalyst in the aliphatic solvent to form acatalyst system, and contacting one or more olefin monomers with thecatalyst system according to the present disclosure. The presentdisclosure further relates to polyolefins formed by a catalyst systemand/or a polymerization process of the present disclosure.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a comparison of ¹H NMR spectra of NOMAH-BF28 activatorsprepared in n-hexane and cyclohexane;

FIG. 2 shows a comparison of ¹¹B NMR spectrum of NOMAH-BF28 ofNOMAH-BF28 activators prepared in n-hexane and cyclohexane; and

FIG. 3 is a graph showing comparative activators in toluene and innon-aromatic solvents.

DETAILED DESCRIPTION Definitions

Unless otherwise noted all melt temperatures (Tm) are DSC second meltand are determined using the following DSC procedure according to ASTMD3418-03. Differential scanning calorimetric (DSC) data are obtainedusing a TA Instruments model Q200 machine. Samples weighing about 5 toabout 10 mg are sealed in an aluminum hermetic sample pan. The DSC dataare recorded by first gradually heating the sample to about 200° C. at arate of about 10° C./minute. The sample is kept at about 200° C. forabout 2 minutes, then cooled to about −90° C. at a rate of about 10°C./minute, followed by an isothermal for about 2 minutes and heating toabout 200° C. at about 10° C./minute. Both the first and second cyclethermal events are recorded. The melting points reported herein areobtained during the second heating/cooling cycle unless otherwise noted.

All molecular weights are weight average (Mw) unless otherwise noted.All molecular weights are reported in g/mol unless otherwise noted. Meltindex (MI) also referred to as 12, reported in g/10 min, is determinedaccording to ASTM D-1238, 190° C., 2.16 kg load. High load melt index(HLMI) also referred to as 121, reported in g/10 min, is determinedaccording to ASTM D-1238, 190° C., 21.6 kg load. Melt index ratio (MIR)is MI divided by HLMI as determined by ASTM D1238.

The specification describes catalysts that can be transition metalcomplexes. The term complex is used to describe molecules in which anancillary ligand is coordinated to a central transition metal atom. Theligand is bulky and stably bonded to the transition metal so as tomaintain its influence during use of the catalyst, such aspolymerization. The ligand may be coordinated to the transition metal bycovalent bond and/or electron donation coordination or intermediatebonds. The transition metal complexes are generally subjected toactivation to perform their polymerization or oligomerization functionusing an activator which is believed to create a cation as a result ofthe removal of an anionic group, often referred to as a leaving group,from the transition metal.

For the purposes of the present disclosure, the numbering scheme for thePeriodic Table Groups is the “New” notation as described in Chemical andEngineering News, 63(5), pg. 27 (1985). Therefore, a “Group 8 metal” isan element from Group 8 of the Periodic Table, e.g., Fe, and so on.

The following abbreviations are used through this specification:

o-biphenyl is an ortho-biphenyl moiety represented by the structure

dme is 1,2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl, Pris propyl, iPr is isopropyl, n-Pr is normal propyl, cPr is cyclopropyl,Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu ispara-tertiary butyl, nBu is normal butyl, sBu is sec-butyl, TMS istrimethylsilyl, TIBAL is triisobutylaluminum, TNOAL istri(n-octyl)aluminum, MAO is methylalumoxane, p-Me is para-methyl, Ph isphenyl, Bn is benzyl (i.e., CH₂Ph), THF (also referred to as thf) istetrahydrofuran, RT is room temperature (and is 25° C. unless otherwiseindicated), tol is toluene, EtOAc is ethyl acetate, MeCy ismethylcyclohexane, and Cy is cyclohexyl.

Unless otherwise indicated (e.g., the definition of “substitutedhydrocarbyl”, etc.), the term “substituted” means that at least onehydrogen atom has been replaced with at least a non-hydrogen group, suchas a hydrocarbyl group, a heteroatom, or a heteroatom containing group,such as halogen (such as Br, Cl, F or I) or at least one functionalgroup such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*,—BR*₂, —SIR*, —SiR*₃, —GeR*, —GeR*₃, —SnR*, —SnR*₃, —PbR*₃, and thelike, where each R* is independently a hydrocarbyl or halocarbylradical, and two or more R* may join together to form a substituted orunsubstituted saturated, partially unsaturated or aromatic cyclic orpolycyclic ring structure, or where at least one heteroatom has beeninserted within a ring structure.

The terms “hydrocarbyl radical,” “hydrocarbyl,” and “hydrocarbyl group,”are used interchangeably throughout this disclosure. Likewise, the terms“group”, “radical”, and “substituent” are also used interchangeably inthis disclosure. For purposes of this disclosure, “hydrocarbyl radical”is defined to be C₁-C₁₀₀ radicals of carbon and hydrogen, that may belinear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.Examples of such radicals can include methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl,hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclooctyl, and the like.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom of the hydrocarbyl radical has been replaced with aheteroatom, or a heteroatom containing group, such as halogen (such asBr, Cl, F or I) or at least one functional group such as —NR*₂, —OR*,—SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*, —BR*₂, —SIR*, —SiR*₃, —GeR*,—GeR*₃, —SnR*, —SnR*₃, —PbR*₃, and the like, where each R* isindependently a hydrocarbyl or halocarbyl radical, and two or more R*may join together to form a substituted or unsubstituted saturated,partially unsaturated or aromatic cyclic or polycyclic ring structure,or where at least one heteroatom has been inserted within a hydrocarbylring.

Substituted cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenylgroups are cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenylgroups where at least one hydrogen atom has been replaced with at leasta non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or aheteroatom containing group, such as halogen (such as Br, Cl, F or I) orat least one functional group such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂,—AsR*₂, —SbR*₂, —SR*, —BR*₂, —SIR*, —SiR*₃, —GeR*, —GeR*₃, —SnR*,—SnR*₃, —PbR*₃, and the like, where each R* is independently ahydrocarbyl or halocarbyl radical, and two or more R* may join togetherto form a substituted or unsubstituted saturated, partially unsaturatedor aromatic cyclic or polycyclic ring structure, or where at least oneheteroatom has been inserted within a ring structure.

Halocarbyl radicals (also referred to as halocarbyls, halocarbyl groupsor halocarbyl substituents) are radicals in which one or morehydrocarbyl hydrogen atoms have been substituted with at least onehalogen (e.g., F, Cl, Br, I) or halogen-containing group (e.g., CF₃).Substituted halocarbyl radicals are radicals in which at least onehalocarbyl hydrogen or halogen atom has been substituted with at leastone functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂,SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like or where at leastone non-carbon atom or group has been inserted within the halocarbylradical such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—,—As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—,—Sn(R*)₂—, —Pb(R*)₂— and the like, where R* is independently ahydrocarbyl or halocarbyl radical provided that at least one halogenatom remains on the original halocarbyl radical. Additionally, two ormore R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

Hydrocarbylsilyl groups, also referred to as silylcarbyl groups, areradicals in which one or more hydrocarbyl hydrogen atoms have beensubstituted with at least one SiR*₃ containing group or where at leastone —Si(R*)₂— has been inserted within the hydrocarbyl radical where R*is independently a hydrocarbyl or halocarbyl radical, and two or more R*may join together to form a substituted or unsubstituted saturated,partially unsaturated or aromatic cyclic or polycyclic ring structure.Silylcarbyl radicals can be bonded via a silicon atom or a carbon atom.

Substituted silylcarbyl radicals are silylcarbyl radicals in which atleast one hydrogen atom has been substituted with at least onefunctional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*,BR*₂, GeR*₃, SnR*₃, PbR₃ and the like or where at least onenon-hydrocarbon atom or group has been inserted within the silylcarbylradical, such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—,—As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Ge(R*)₂—, —Sn(R*)₂—,—Pb(R*)₂— and the like, where R* is independently a hydrocarbyl orhalocarbyl radical, and two or more R* may join together to form asubstituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure.

Germylcarbyl radicals (also referred to as germylcarbyls, germylcarbylgroups or germylcarbyl substituents) are radicals in which one or morehydrocarbyl hydrogen atoms have been substituted with at least one GeR*₃containing group or where at least one —Ge(R*)₂— has been insertedwithin the hydrocarbyl radical where R* is independently a hydrocarbylor halocarbyl radical, and two or more R* may join together to form asubstituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure. Germylcarbyl radicals canbe bonded via a germanium atom or a carbon atom.

Substituted germylcarbyl radicals are germylcarbyl radicals in which atleast one hydrogen atom has been substituted with at least onefunctional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*,BR*₂, SiR*₃, SnR*₃, PbR₃ and the like or where at least onenon-hydrocarbon atom or group has been inserted within the germylcarbylradical, such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—,—As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Sn(R*)₂—,—Pb(R*)₂— and the like, where R* is independently a hydrocarbyl orhalocarbyl radical, and two or more R* may join together to form asubstituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure.

The terms “alkyl radical,” “alkyl moiety”, and “alkyl” are usedinterchangeably throughout this disclosure. For purposes of thisdisclosure, “alkyl radicals” are defined to be C₁-C₁₀₀ alkyls that maybe linear, branched, or cyclic. Examples of such radicals can includemethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cyclooctyl, and the like. Substituted alkylradicals are radicals in which at least one hydrogen atom of the alkylradical has been substituted with at least a non-hydrogen group, such asa hydrocarbyl group, a heteroatom, or a heteroatom containing group,such as halogen (such as Br, Cl, F or I) or at least one functionalgroup such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*,—BR*₂, —SIR*, —SiR*₃, —GeR*, —GeR*₃, —SnR*, —SnR*₃, —PbR*₃, and thelike, where each R* is independently a hydrocarbyl or halocarbylradical, and two or more R* may join together to form a substituted orunsubstituted saturated, partially unsaturated or aromatic cyclic orpolycyclic ring structure, or where at least one heteroatom has beeninserted within a hydrocarbyl ring.

The term “branched alkyl” means that the alkyl group contains a tertiaryor quaternary carbon (a tertiary carbon is a carbon atom bound to threeother carbon atoms. A quaternary carbon is a carbon atom bound to fourother carbon atoms). For example, 3,5,5 trimethylhexylphenyl is an alkylgroup (hexyl) having three methyl branches (hence, one tertiary and onequaternary carbon) and thus is a branched alkyl bound to a phenyl group.

The term “alkenyl” means a straight-chain, branched-chain, or cyclichydrocarbon radical having one or more carbon-carbon double bonds. Thesealkenyl radicals may be substituted. Examples of suitable alkenylradicals can include ethenyl, propenyl, allyl, 1,4-butadienylcyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyland the like.

The term “arylalkenyl” means an aryl group where a hydrogen has beenreplaced with an alkenyl or substituted alkenyl group. For example,styryl indenyl is an indene substituted with an arylalkenyl group (astyrene group).

The term “alkoxy”, “alkoxyl”, or “alkoxide” means an alkyl ether or arylether radical wherein the terms alkyl and aryl are as defined herein.Examples of suitable alkyl ether radicals can include methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy,phenoxy, and the like.

The term “aryloxy” or “aryloxide” means an aryl ether radical whereinthe term aryl is as defined herein.

The term “aryl” or “aryl group” means a carbon-containing aromatic ringsuch as phenyl. Likewise, heteroaryl means an aryl group where a ringcarbon atom (or two or three ring carbon atoms) has been replaced with aheteroatom, such as N, O, or S. As used herein, the term “aromatic” alsorefers to pseudoaromatic heterocycles which are heterocyclicsubstituents that have similar properties and structures (nearly planar)to aromatic heterocyclic ligands, but are not by definition aromatic.

Heterocyclic means a cyclic group where a ring carbon atom (or two orthree ring carbon atoms) has been replaced with a heteroatom, such as N,O, or S. A heterocyclic ring is a ring having a heteroatom in the ringstructure as opposed to a heteroatom substituted ring where a hydrogenon a ring atom is replaced with a heteroatom. For example,tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl isa heteroatom substituted ring.

Substituted heterocyclic means a heterocyclic group where at least onehydrogen atom of the heterocyclic radical has been substituted with atleast a non-hydrogen group, such as a hydrocarbyl group, a heteroatom,or a heteroatom containing group, such as halogen (such as Br, Cl, F orI) or at least one functional group such as —NR*₂, —OR*, —SeR*, —TeR*,—PR*₂, —AsR*₂, —SbR*₂, —SR*, —BR*₂, —SIR*, —SiR*₃, —GeR*, —GeR*₃, —SnR*,—SnR*₃, —PbR*₃, and the like, where each R* is independently ahydrocarbyl or halocarbyl radical.

A substituted aryl is an aryl group where at least one hydrogen atom ofthe aryl radical has been substituted with at least a non-hydrogengroup, such as a hydrocarbyl group, a heteroatom, or a heteroatomcontaining group, such as halogen (such as Br, Cl, F or I) or at leastone functional group such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂,—SbR*₂, —SR*, —BR*₂, —SIR*, —SiR*₃, —GeR*, —GeR*₃, —SnR*, —SnR*₃,—PbR*₃, and the like, where each R* is independently a hydrocarbyl orhalocarbyl radical, and two or more R* may join together to form asubstituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure, or where at least oneheteroatom has been inserted within a hydrocarbyl ring, for example3,5-dimethylphenyl is a substituted aryl group.

The term “substituted phenyl,” or “substituted phenyl group” means aphenyl group having one or more hydrogen groups replaced by ahydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatomcontaining group, such as halogen (such as Br, Cl, F or I) or at leastone functional group such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂,—SbR*₂, —SR*, —BR*₂, —SIR*, —SiR*₃, —GeR*, —GeR*₃, —SnR*, —SnR*₃,—PbR*₃, and the like, where each R* is independently a hydrocarbyl,halogen, or halocarbyl radical. Preferably the “substituted phenyl”group is represented by the formula:

where each of R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is independently selected fromhydrogen, C₁-C₄₀ hydrocarbyl or C₁-C₄₀ substituted hydrocarbyl, aheteroatom, such as halogen, or a heteroatom-containing group (providedthat at least one of R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is not H), or acombination thereof.

A “fluorophenyl” or “fluorophenyl group” is a phenyl group substitutedwith one, two, three, four or five fluorine atoms.

The term “arylalkyl” means an aryl group where a hydrogen has beenreplaced with an alkyl or substituted alkyl group. For example,3,5′-di-tert-butyl-phenyl indenyl is an indene substituted with anarylalkyl group. When an arylalkyl group is a substituent on anothergroup, it is bound to that group via the aryl. For example in FormulaAI, the aryl portion is bound to E.

The term “alkylaryl” means an alkyl group where a hydrogen has beenreplaced with an aryl or substituted aryl group. For example, phenethylindenyl is an indene substituted with an ethyl group bound to a benzenegroup. When an alkylaryl group is a substituent on another group, it isbound to that group via the alkyl.

Reference to an alkyl, alkenyl, alkoxide, or aryl group withoutspecifying a particular isomer (e.g., butyl) expressly discloses allisomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl), unlessotherwise indicated.

The term “ring atom” means an atom that is part of a cyclic ringstructure. Accordingly, a benzyl group has six ring atoms andtetrahydrofuran has 5 ring atoms.

For purposes of the present disclosure, a “catalyst system” is acombination of at least one catalyst compound, an activator, and anoptional support material. The catalyst systems may further comprise oneor more additional catalyst compounds. For the purposes of the presentdisclosure, when catalyst systems are described as comprising neutralstable forms of the components, it is well understood by one of ordinaryskill in the art, that the ionic form of the component is the form thatreacts with the monomers to produce polymers. Catalysts of the presenteddisclosure and activators represented by formula (I) are intended toembrace ionic forms in addition to the neutral forms of the compounds.

“Complex” as used herein, is also often referred to as catalystprecursor, precatalyst, catalyst, catalyst compound, transition metalcompound, or transition metal complex. These words are usedinterchangeably.

A scavenger is a compound that is typically added to facilitatepolymerization by scavenging impurities. Some scavengers may also act asactivators and may be referred to as co-activators. A co-activator, thatis not a scavenger, may also be used in conjunction with an activator inorder to form an active catalyst. In some embodiments a co-activator canbe pre-mixed with the transition metal compound to form an alkylatedtransition metal compound.

In the description herein, a catalyst may be described as a catalystprecursor, a precatalyst compound, a catalyst compound or a transitionmetal compound, and these terms are used interchangeably. Apolymerization catalyst system is a catalyst system that can polymerizemonomers into polymer. An “anionic ligand” is a negatively chargedligand which donates one or more pairs of electrons to a metal ion. A“neutral donor ligand” is a neutrally charged ligand which donates oneor more pairs of electrons to a metal ion.

A metallocene catalyst is defined as an organometallic compound with atleast one t-bound cyclopentadienyl moiety or substitutedcyclopentadienyl moiety (such as substituted or unsubstituted Cp, Ind,or Flu) and more frequently two (or three) t-bound cyclopentadienylmoieties or substituted cyclopentadienyl moieties (such as substitutedor unsubstituted Cp, Ind, or Flu). (Cp=cyclopentadienyl, Ind=indenyl,Flu=fluorenyl).

For purposes of the present disclosure, in relation to catalystcompounds, the term “substituted” means that a hydrogen group has beenreplaced with a hydrocarbyl group, a heteroatom, or a heteroatomcontaining group. For example, methyl cyclopentadiene (Cp) is a Cp groupsubstituted with a methyl group.

“Catalyst productivity” is a measure of how many grams of polymer (P)are produced using a polymerization catalyst comprising W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing formula: P/(T×W) and expressed in units of gPgcat⁻¹ hr⁻¹.“Conversion” is the amount of monomer that is converted to polymerproduct, and is reported as mol % and is calculated based on the polymeryield and the amount of monomer fed into the reactor. “Catalystactivity” is a measure of the level of activity of the catalyst and isreported as the mass of product polymer (P) produced per mole (or mmol)of catalyst (cat) used (kgP/molcat or gP/mmolCat), and catalyst activitycan also be expressed per unit of time, for example, per hour (hr),e.g., (Kg/mmol h).

For purposes herein an “olefin,” alternatively referred to as “alkene,”is a linear, branched, or cyclic compound comprising carbon and hydrogenhaving at least one double bond. For purposes of this specification andthe claims appended thereto, when a polymer or copolymer is referred toas comprising an olefin, the olefin present in such polymer or copolymeris the polymerized form of the olefin. For example, when a copolymer issaid to have a “propylene” content of 35 wt % to 55 wt %, it isunderstood that the mer unit in the copolymer is derived from propylenein the polymerization reaction and the derived units are present at 35wt % to 55 wt %, based upon the weight of the copolymer.

For purposes herein a “polymer” has two or more of the same or differentmonomer (“mer”) units. A “homopolymer” is a polymer having mer unitsthat are the same. A “copolymer” is a polymer having two or more merunits that are different from each other. A “terpolymer” is a polymerhaving three mer units that are different from each other. “Different”in reference to mer units indicates that the mer units differ from eachother by at least one atom or are different isomerically. Accordingly,copolymer, as used herein, can include terpolymers and the like. Anoligomer is typically a polymer having a low molecular weight, such anMn of less than 25,000 g/mol, or less than 2,500 g/mol, or a low numberof mer units, such as 75 mer units or less or 50 mer units or less. An“ethylene polymer” or “ethylene copolymer” is a polymer or copolymercomprising at least 50 mole % ethylene derived units, a “propylenepolymer” or “propylene copolymer” is a polymer or copolymer comprisingat least 50 mole % propylene derived units, and so on.

As used herein, Mn is number average molecular weight, Mw is weightaverage molecular weight, and Mz is z average molecular weight, wt % isweight percent, and mol % is mole percent. Molecular weight distribution(MWD), also referred to as polydispersity index (PDI), is defined to beMw divided by Mn.

The term “continuous” means a system that operates without interruptionor cessation for a period of time, such as where reactants arecontinually fed into a reaction zone and products are continually orregularly withdrawn without stopping the reaction in the reaction zone.For example, a continuous process to produce a polymer would be onewhere the reactants are continually introduced into one or more reactorsand polymer product is continually withdrawn.

A “solution polymerization” means a polymerization process in which thepolymerization is conducted in a liquid polymerization medium, such asan inert solvent or monomer(s) or their blends. A solutionpolymerization is typically homogeneous. A homogeneous polymerization isone where the polymer product is dissolved in the polymerization medium.Such systems are typically not turbid as described in Oliveira, J. V. etal. (2000) “High-Pressure Phase Equilibria for Polypropylene-HydrocarbonSystems,” Ind. Eng. Chem. Res., v. 39, pp. 4627-4633.

A bulk polymerization means a polymerization process in which themonomers and/or comonomers being polymerized are used as a solvent ordiluent using little or no inert solvent or diluent. A small fraction ofinert solvent might be used as a carrier for catalyst and scavenger. Abulk polymerization system contains less than about 25 wt % of inertsolvent or diluent, such as less than about 10 wt %, such as less thanabout 1 wt %, such as 0 wt %.

DESCRIPTION

The present disclosure relates to a process to produce activatorcompounds in alphatic and/or alicyclic hydrocarbon solvents that can beused in olefin polymerization processes. For example, the presentdisclosure provides activators, catalyst systems comprising catalystcompounds and activators, and processes for polymerizing olefins usingsaid catalyst systems. In the present disclosure, activators aredescribed that feature anilinium groups with long-chain (i.e., havinggreater than or equal to 6 carbon atoms) aliphatic hydrocarbyl groupsfor improved solubility of the activator in aliphatic and/or alicyclicsolvents, as compared to conventional activator compounds.

The present disclosure relates to activator compounds that can be usedin olefin polymerization processes. For example, the present disclosureprovides anilinium borate activators, catalyst systems comprisinganilinium borate activators, and processes for polymerizing olefinsusing anilinium borate activators. In the present disclosure, activatorsare described that feature anilinium groups substituted with at leastone aliphatic hydrocarbon group having greater than or equal to 6 carbonatoms, preferably linear C₆-C₅₀ alkyl radicals for improved solubilityof the activator in aliphatic solvents, as compared to conventionalactivator compounds.

Useful borate groups of the present disclosure include fluoroarylborates. It has been discovered that activators of the presentdisclosure having fluorophenyl, or fluoronaphthyl borate anions haveimproved solubility in aliphatic solvents, as compared to conventionalactivator compounds, which are typically insoluble in these samealiphatic and alicyclic solvents. Activators of the present disclosurecan provide polyolefins having a weight average molecular weight (Mw) ofabout 100,000 or greater and a melt temperature (Tm) of about 110° C. orgreater. Further, activators having a cation having at least one methylgroup, and at least one C₆ to C₅₀ or C₁₀ to C₅₀ linear alkyl group canprovide enhanced activity for polymerization.

In embodiments, a process to produce an activator compound comprises thesteps of contacting a compound according to formula (A) with a compoundhaving the general formula M-(BR⁴R⁵R⁶R⁷) in an aliphatic hydrocarbonsolvent, an alicyclic hydrocarbon solvent, or a combination thereof, ata reaction temperature and for a period of time sufficient to produce amixture comprising the activator compound according to formula (I) and asalt having the formula M(X); wherein formula (A) is represented by:

wherein formula (I) is represented by:

wherein in each of formulae (A) and (I): each of R¹, R², R⁸, R⁹, R¹⁰,R¹¹, and R¹² is independently a hydrogen or a C₁-C₄₀ linear alkyl; R¹,R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² together comprise 15 or more carbon atoms;each of R⁴, R⁵, R⁶, and R⁷ comprises an aromatic hydrocarbon having from6 to 24 carbon atoms; at least one of R⁴, R⁵, R⁶, and R⁷ is substitutedwith one or more fluorine atoms; X is halogen; and M is a Group 1 metal.

In one or more embodiments, at least one of R⁴, R⁵, R⁶, and R⁷ comprisesa perfluoro substituted phenyl moiety, a perfluoro substituted naphthylmoiety, a perfluoro substituted biphenyl moiety, a perfluoro substitutedtriphenyl moiety, or a combination thereof. In one or more embodiments,R⁴, R⁵, R⁶, and R⁷ are perfluoro substituted phenyl radicals. In one ormore embodiments, R⁴, R⁵, R⁶, and R⁷ are perfluoro substituted naphthylradicals. In one or more embodiments, R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹²together comprise 20 or more carbon atoms, or 30 or more carbon atoms.

In one or more embodiments, each of R⁴, R⁵, R⁶, and R⁷ is independentlya hydride, bridged or unbridged dialkylamido, halide, alkoxide,aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, or halosubstituted-hydrocarbyl radical, provided that whenone or more of R⁴, R⁵, R⁶, and R⁷ is a fluorophenyl group, then R² isnot a C₁-C₄₀ linear alkyl group, preferably R² is not an optionallysubstituted C₁-C₄₀ linear alkyl group (alternately when each of R⁴, R⁵,R⁶, and R⁷ are substituted phenyl group, then R² is not a C₁-C₄₀ linearalkyl group, preferably R² is not an optionally substituted C₁-C₄₀linear alkyl group). Preferably, when each of R⁴, R⁵, R⁶, and R⁷ areeach fluorophenyl group (alternately when each of R⁴, R⁵, R⁶, and R⁷ isa substituted phenyl group), then R² is a meta- and/or para-substitutedphenyl group, where the meta and para substituents are, independently,an optionally substituted C₁ to C₄₀ hydrocarbyl group (such as a C₆ toC₄₀ aryl group or linear alkyl group, a C₁₂ to C₃₀ aryl group or linearalkyl group, or a C₁₀ to C₂₀ aryl group or linear alkyl group), anoptionally substituted alkoxy group, or an optionally substituted silylgroup. Preferably, each of R⁴, R⁵, R⁶, and R⁷ is a fluorinatedhydrocarbyl group having 1 to 30 carbon atoms, more preferably each ofR⁴, R⁵, R⁶, and R⁷ is a fluorinated aryl (such as phenyl or naphthyl)group, and most preferably each of R⁴, R⁵, R⁶, and R⁷ is aperflourinated aryl (such as phenyl or naphthyl) group. Examples ofsuitable [BR⁴ R⁵R⁶R⁷]− also include diboron compounds as disclosed inU.S. Pat. No. 5,447,895, which is fully incorporated herein byreference. Preferably at least one of R⁴, R⁵, R⁶, and R⁷ is notsubstituted phenyl, preferably all of R⁴, R⁵, R⁶, and R⁷ are notsubstituted phenyl. Preferably at least one each of R⁴, R⁵, R⁶, and R⁷is not perfluorophenyl, preferably all of R⁴, R⁵, R⁶, and R⁷ are notperfluorophenyl.

In one or more embodiments, two of more of R¹, R², R⁸, R⁹, R¹⁰, R¹¹, andR¹² are each a C₁₀-C₄₀ linear alkyl radical, or a C₁₀-C₂₂ linear alkylradical. In one or more embodiments, two or more of R¹, R², and R¹⁰ areeach a C₁₀-C₄₀ linear alkyl, or two or more of R¹, R², and R¹⁰ are eacha C₁₀-C₂₂ linear alkyl.

In one or more embodiments, at least one of R⁸, R⁹, R¹⁰, R¹¹, and R¹² isa linear alkyl radical comprising 6 or more carbon atoms. In one or moreembodiments, R¹⁰ is a linear alkyl radical comprising 6 or more carbonatoms. In some embodiments, R¹ is methyl and each of R² and R¹⁰ isC₆-C₄₀ linear alkyl radical.

In one or more embodiments, one, two, three, four or five of R⁸, R⁹,R¹⁰, R¹¹, and R¹² is not hydrogen.

In one or more embodiments, one, two, or three of R⁹, R¹⁰, and R¹¹ isnot hydrogen.

In one or more embodiments R⁸ and R¹² are hydrogen.

In one or more embodiments, one, two, or three of R⁹, R¹⁰, and R¹¹ isnot hydrogen R⁸ and R¹² are hydrogen.

In one or more embodiments, the process further comprises the step offiltering the mixture to remove the salt to produce a clear homogeneoussolution comprising the activator compound according to formula (I) andoptionally removing at least a portion of the solvent.

In one or more embodiments of the process, the reaction temperature isless than or equal to the reflux temperature of the solvent atatmospheric pressure and the time is less than or equal to about 24hours, preferably the reaction temperature is from about 20° C. to lessthan or equal to about 50° C., and the time is less than or equal toabout 2 hours.

In one or more embodiments of the process, the reaction solvent ishexane, isohexane, cyclohexane, methylcyclohexane, or a combinationthereof. In embodiments a 1 millimole per liter mixture of the activatorcompound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or acombination thereof, forms a clear homogeneous solution at 25° C. Insome embodiments of the process a 1 millimole per liter mixture of theactivator compound in n-hexane or isohexane forms a clear homogeneoussolution at 25° C.

In one or more embodiments of the process a 10 millimole per litermixture or a 20 millimolar per liter mixture of the activator compoundin n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combinationthereof, forms a clear homogeneous solution at 25° C. In someembodiments of the process a 10 millimole per liter mixture or a 20millimolar per liter mixture of the activator compound in n-hexane orisohexane forms a clear homogeneous solution at 25° C.

The present disclosure relates to a catalyst system comprising atransition metal compound and an activator compound as described herein,to the use of such activator compounds for activating a transition metalcompound in a catalyst system for polymerizing olefins, and to processesfor polymerizing olefins, the process comprising contacting underpolymerization conditions one or more olefins with a catalyst systemcomprising a transition metal compound and such activator compounds,where aromatic solvents, such as toluene, are absent (e.g. present atzero mol %, alternately present at less than 1 mol %, preferably thecatalyst system, the polymerization reaction and/or the polymer producedare free of “detectable aromatic hydrocarbon solvent,” such as toluene.For purposes of the present disclosure, “detectable aromatic hydrocarbonsolvent” means 0.1 mg/m² or more as determined by gas phasechromatography. For purposes of the present disclosure, “detectabletoluene” means 0.1 mg/m² or more as determined by gas phasechromatography.

The polyolefins produced herein preferably contain 0 ppm of aromatichydrocarbon. Preferably, the polyolefins produced herein contain 0 ppmof toluene.

The catalyst systems used herein preferably contain 0 ppm of aromatichydrocarbon. Preferably, the catalyst systems used herein contain 0 ppmof toluene.

In one or more embodiments, a catalyst system comprises a catalyst andthe activator compound produced according to one or more embodiments ofthe instant disclosure. In some embodiments, the catalyst system furthercomprises a support material. In some embodiments, the catalyst isrepresented by formula (II) or formula (III):

wherein in each of formula (II) and formula (III): M is the metalcenter, and is a Group 4 metal; n is 0 or 1; T is an optional bridginggroup selected from dialkylsilyl, diarylsilyl, dialkylmethyl, ethylenylor hydrocarbylethylenyl wherein one, two, three or four of the hydrogenatoms in ethylenyl are substituted by hydrocarbyl; Z is nitrogen,oxygen, sulfur, or phosphorus (preferably nitrogen); q is 1 or 2(preferably q is 1 when Z in N); R′ is a C₁-C₄₀ alkyl or substitutedalkyl group, preferably a linear C₁-C₄₀ alkyl or substituted alkylgroup; X₁ and X₂ are, independently, hydrogen, halogen, hydrideradicals, hydrocarbyl radicals, substituted hydrocarbyl radicals,halocarbyl radicals, substituted halocarbyl radicals, silylcarbylradicals, substituted silylcarbyl radicals, germylcarbyl radicals, orsubstituted germylcarbyl radicals; or both X₁ and X₂ are joined andbound to the metal atom to form a metallacycle ring containing fromabout 3 to about 20 carbon atoms; or both together can be an olefin,diolefin or aryne ligand.

In some embodiments, the catalyst of the catalyst system is one or moreof: bis(1-methyl, 3-n-butyl cyclopentadienyl) M(R)₂; dimethylsilylbis(indenyl)M(R)₂; bis(indenyl)M(R)₂; dimethylsilylbis(tetrahydroindenyl)M(R)₂; bis(n-propylcyclopentadienyl)M(R)₂;dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M(R)₂;dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M(R)₂;dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M(R)₂;dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M(R)₂;μ-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)M(R)₂;μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M(R)₂;μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M(R)₂;μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)M(R)₂;μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂;μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂;μ-(CH₃)₂Si(η⁵-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)M(R)₂;where M is selected from Ti, Zr, and Hf; and R is selected from halogenor C₁ to C₅ alkyl.

In embodiments a process of polymerizing olefins to produce at least onepolyolefin comprises the steps of contacting at least one olefin withthe catalyst system according to one or more embodiments of the instantdisclosure and obtaining a polyolefin. In some embodiments, at least oneolefin is propylene and the polyolefin is isotactic polypropylene. Inalterative embodiments, the polymerization process comprises contactingtwo or more different olefins with the catalyst system and obtaining apolyolefin. In some embodiments, the two or more olefins are ethyleneand propylene and/or the two or more olefins further comprise a diene.

Non-Coordinating Anion (NCA) Activators

Noncoordinating anion (NCA) means an anion either that does notcoordinate to the catalyst metal cation or that does coordinate to themetal cation, but only weakly. The term NCA is also defined to includemulticomponent NCA-containing activators, such asN,N-dioctadecylanilinium tetrakis(perfluoronaphthyl)borate, that containan acidic cationic group and the non-coordinating anion. The term NCA isalso defined to include neutral Lewis acids, such astris(pentafluoronaphthyl)boron, that can react with a catalyst to forman activated species by abstraction of an anionic group. An NCAcoordinates weakly enough that a neutral Lewis base, such as anolefinically or acetylenically unsaturated monomer can displace it fromthe catalyst center. Any metal or metalloid that can form a compatible,weakly coordinating complex may be used or contained in thenoncoordinating anion. Suitable metals can include aluminum, gold, andplatinum. Suitable metalloids can include boron, aluminum, phosphorus,and silicon. The term non-coordinating anion activator includes neutralactivators, ionic activators, and Lewis acid activators.

“Compatible” non-coordinating anions can be those which are not degradedto neutrality when the initially formed complex decomposes. Further, theanion will not transfer an anionic substituent or fragment to the cationso as to cause it to form a neutral transition metal compound and aneutral by-product from the anion. Non-coordinating anions useful inaccordance with the present disclosure are those that are compatible,stabilize the transition metal cation in the sense of balancing itsionic charge at +1, and yet retain sufficient lability to permitdisplacement during polymerization.

Activators

The present disclosure provides activators, such as anilinium metallateor metalloid activator compounds, comprising anilinium groups withlong-chain aliphatic hydrocarbyl groups combined with metallate ormetalloid anions, such as borates or aluminates. When an activator ofthe present disclosure is used with a catalyst compound (such as a group4 metallocene compound) in an olefin polymerization, a polymer can beformed having a higher molecular weight and melt temperature thanpolymers formed using comparative activators. Likewise, when anactivator of the present disclosure where R¹ is methyl is used with agroup 4 metallocene catalyst in an olefin polymerization, the catalystsystem activity is substantially better than comparative activators, andcan form polymers having a higher molecular weight and/or melttemperature vs. polymers formed using comparative activators. Inaddition, it has been discovered that activators of the presentdisclosure are soluble in aliphatic and/or alicyclic solvents.

In at least one embodiment of the invention, the activator produced bythe process is represented by formula (I):

wherein B is boron and each of R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² isindependently a hydrogen or a C₁-C₄₀ linear alkyl. In embodiments, R¹,R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² together comprise 10 or more carbon atoms,or 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20or more carbon atoms, such as 22 or more carbon atoms, such as 25 ormore carbon atoms, such as 30 or more carbon atoms, such as 35 or morecarbon atoms, such as 40 or more carbon atoms. In at least oneembodiment, R¹ and R² are independently C₁-C₂₂-alkyl. In embodiments,each of R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹², is independently selectedfrom hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-butadecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,n-nonadecyl, and n-icosyl; and each of R⁴, R⁵, R⁶, and R⁷ isindependently phenyl or naphthyl, wherein at least one of R⁴, R⁵, R⁶,and R⁷ is phenyl substituted with from one to five fluorine atoms,and/or or naphthyl substituted with from one to seven fluorine atoms.

Preferably at least one of R⁴, R⁵, R⁶, and R⁷ is a fluorinatedhydrocarbyl group having 1 to 30 carbon atoms, more preferably each is afluorinated aryl (such as phenyl or naphthyl) group, and most preferablyeach is a perfluorinated aryl (such as phenyl or naphthyl) group.

In any embodiment described herein, preferably each of R⁴, R⁵, R⁶, andR⁷ is independently a naphthyl comprising one fluorine atom, twofluorine atoms, three fluorine atoms, four fluorine atoms, five fluorineatoms, six fluorine atoms, or seven fluorine atoms, preferably sevenfluorine atoms. In any embodiment described herein, preferably each ofR⁴, R⁵, R⁶, and R⁷ is independently a phenyl comprising one fluorineatom, two fluorine atoms, three fluorine atoms, four fluorine atoms, orfive fluorine atoms, preferably five fluorine atoms.

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds of the present disclosure by converting the neutralcatalyst compound to a catalytically active catalyst compound cation.

Catalyst systems of the present disclosure may be formed by combiningthe catalysts with activators in any suitable manner, including bysupporting them for use in slurry or gas phase polymerization. Thecatalyst systems may also be added to or generated in solutionpolymerization or bulk polymerization (in the monomer, i.e., little orno solvent).

Both the cation part of formula (I) as well as the anion part thereof,which is an NCA, will be further illustrated below. Any combinations ofcations and NCAs disclosed herein are suitable to be used in theprocesses of the present disclosure and are thus incorporated herein.

Activators—the Cations

The cation component of the activators described herein (such as thoseof formula (I), is a protonated Lewis base that can be capable ofprotonating a moiety, such as an alkyl or aryl, from the transitionmetal compound. Thus, upon release of a neutral leaving group (e.g. analkane resulting from the combination of a proton donated from thecationic component of the activator and an alkyl substituent of thetransition metal compound) transition metal cation results, which is thecatalytically active species.

In at least one embodiment of formula (I), where the cation is:

wherein each of R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independentlyC₁-C₄₀ linear alkyl and together comprise 15 or more carbon atoms, suchas 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22or more carbon atoms, such as 25 or more carbon atoms, such as 30 ormore carbon atoms, such as 35 or more carbon atoms, such as 37 or morecarbon atoms, such as 40 or more carbon atoms, such as 45 or more carbonatoms. In at least one embodiment, at least one of R¹, R², R⁸, R⁹, R¹⁰,R¹¹, and R¹² are independently substituted or unsubstituted C₁-C₂₂linear alkyl, preferably selected from methyl, ethyl, n-propyl, n-butyl,n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl,n-dodecyl, n-tridecyl, n-butadecyl, n-pentadecyl, n-hexadecyl,n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl. In a preferredembodiment, R¹ is methyl, R² is C₁₀ to C₃₀ linear alkyl. Preferably R⁸,R⁹, R¹¹, and R¹² is hydrogen, i.e., not orthro or meta substitutedphenyl.

In a preferred embodiment, R¹ is methyl, R² is C₁ to C₃₅ linear alkyland R⁸ is C₁₀ to C₃₀ linear alkyl such as n-decyl, n-undecyl, n-dodecyl,n-tridecyl, n-butadecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl,n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl;n-tetracosyl, n-pentacosyl; n-hexacosyl; n-heptacosyl, n-octacosyl,n-nonacosyl, n-triacontyl.

In a preferred embodiment, R¹ is methyl, R² is C₁ to C₃₅ linear alkyland R¹⁰ is a C₁₀ to C₃₀ linear alkyl, such as n-decyl, n-undecyl,n-dodecyl, n-tridecyl, n-butadecyl, n-pentadecyl, n-hexadecyl,n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl,n-docosyl, n-tricosyl; n-tetracosyl, n-pentacosyl; n-hexacosyl;n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl.

Preferably, the cation is represented by the formula (Ia):

Activators—the Anion

In at least one embodiment, in the borate moiety ([BR⁴R⁵R⁶R⁷]—) of theactivator represented by formula (I), each of R⁴, R⁵, R⁶, and R⁷ isindependently aryl (such as phenyl or naphthyl or bi-phenyl), wherein atleast one of R⁴, R⁵, R⁶, and R⁷ is substituted with from one to five orfrom one to seven fluorine atoms. In at least one embodiment, each ofR⁴, R⁵, R⁶, and R⁷ is phenyl, wherein at least one of R⁴, R⁵, R⁶, and R⁷is substituted with from one to five fluorine atoms. In at least oneembodiment, each of R⁴, R⁵, R⁶, and R⁷ is naphthyl, wherein at least oneof R⁴, R⁵, R⁶, and R⁷ is substituted with from one to seven fluorineatoms.

In at least one embodiment, each of R⁴, R⁵, R⁶, and R⁷ is independentlynaphthyl comprising one fluorine atom, two fluorine atoms, threefluorine atoms, four fluorine atoms, five fluorine atoms, six fluorineatoms, or seven fluorine atoms.

In at least one embodiment, each of R⁴, R⁵, R⁶, and R⁷ is independentlyphenyl comprising one fluorine atom, two fluorine atoms, three fluorineatoms, four fluorine atoms, or five fluorine atoms. In one embodiment,the borate activator comprises tetrakis(heptafluoronaphth-2-yl)borate.

Preferred anions for use in the non-coordinating anion activatorsdescribed herein include those represented by formula (7) below:

wherein:

M* is a group 13 atom, preferably B or Al, preferably B;

each R¹¹ is, independently, a halide, preferably a fluoride;

each R¹² is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R^(a), whereR^(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group, preferablyR¹² is a fluoride or a perfluorinated phenyl group;

each R¹³ is a halide, a C₆ to C₂₀ substituted aromatic hydrocarbyl groupor a siloxy group of the formula —O—Si—R_(a), where R^(a) is a C₁ to C₂₀hydrocarbyl or hydrocarbylsilyl group, preferably R¹³ is a fluoride or aC₆ perfluorinated aromatic hydrocarbyl group;

wherein R¹² and R¹³ can form one or more saturated or unsaturated,substituted or unsubstituted rings, preferably R¹² and R¹³ form aperfluorinated phenyl ring. Preferably the anion has a molecular weightof greater than 700 g/mol, and, preferably, at least three of thesubstituents on the M* atom each have a molecular volume of greater than180 cubic A.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in Girolami, G. S. (1994)“A Simple “Back of the Envelope” Method for Estimating the Densities andMolecular Volumes of Liquids and Solids,” Journal of Chemical Education,v. 71(11), November 1994, pp. 962-964. Molecular volume (MV), in unitsof cubic A, is calculated using the formula: MV=8.3V_(S), where V_(S) isthe scaled volume. V_(S) is the sum of the relative volumes of theconstituent atoms, and is calculated from the molecular formula of thesubstituent using Table 1 below of relative volumes. For fused rings,the V_(S) is decreased by 7.5% per fused ring. The Calculated Total MVof the anion is the sum of the MV per substituent, for example, the MVof perfluorophenyl is 183 Å³, and the Calculated Total MV fortetrakis(perfluorophenyl)borate is four times 183 Å³, or 732 Å³.

TABLE 1 Element Relative Volume H 1 1^(st) short period, Li to F 22^(nd) short period, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd)long period, Rb to I 7.5 3^(rd) long period, Cs to Bi 9

Exemplary anions useful herein and their respective scaled volumes andmolecular volumes are shown in Table 2 below. The dashed bonds indicatebonding to boron.

TABLE 2 Molecular MV Formula of Per Calculated Each subst. Total MV IonStructure of Boron Substituents Substituent V_(s) (Å³) (Å³)tetrakis(perfluorophenyl)borate

C₆F₅ 22 183 732 tris(perfluorophenyl)- (perfluoronaphthyl)borate

C₆F₅ C₁₀F₇ 22 34 183 261 810 (perfluorophenyl)tris-(perfluoronaphthyl)borate

C₆F₅ C₁₀F₇ 22 34 183 261 966 tetrakis(perfluoronaphthyl)borate

C₁₀F₇ 34 261 1044 tetrakis(perfluorobiphenyl)borate

C₁₂F₉ 42 349 1396 [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 62 515 2060

The activators may be added to a polymerization in the form of an ionpair in which the cation reacts with a basic leaving group on thetransition metal complex to form a transition metal complex cation and[NCA]-.

In at least one embodiment, an activator of the present disclosure, whencombined with a group 4 metallocene catalyst compound to form an activeolefin polymerization catalyst, produces a higher molecular weightpolymer (e.g., Mw) than comparative activators that use other borateanions.

In at least one embodiment, an activator of the present disclosure whereR¹ is methyl, when combined with a group 4 metallocene to form an activeolefin polymerization catalyst, produces a higher molecular weightpolymer (e.g., Mw) than comparative activators that use other borateanions.

The typical activator-to-catalyst ratio, e.g., all NCAactivators-to-catalyst ratio is about a 1:1 molar ratio. Alternatepreferred ranges include from 0.1:1 to 100:1, alternately from 0.5:1 to200:1, alternately from 1:1 to 500:1 alternately from 1:1 to 1000:1. Aparticularly useful range is from 0.5:1 to 10:1, preferably 1:1 to 5:1.

It is also within the scope of the present disclosure that the catalystcompounds can be combined with combinations of alumoxanes and theactivators described herein.

Synthesis

In at least one embodiment, the general synthesis of the activators canbe performed using a two-step process. In the first step, the anilinecompound is dissolved in a C₄-C₂₀ aliphatic or alicycle solvent,preferably hexane, isohexane, cyclohexane, and/or methylcyclohexane, andan excess (e.g., 1.2 molar equivalents) of hydrogen chloride or hydrogenbromide is added to form an anilinium halide salt. This salt is may beisolated by filtration from the reaction medium and dried under reducedpressure. The halide salt is then contacted with about one molarequivalent of an alkali metal (Group 1 metal) metallate or metalloid(such as a borate or aluminate) in an aliphatic or alicyclic solvent(e.g. pentane, hexane, isohexane, cyclohexane, and/or methylcyclohexane), to form the desired borate or aluminate along withbyproduct alkali metal halide salt (e.g., NaCl), the latter of which cantypically be removed by filtration.

In embodiments, the anilinium halide, typically a chloride, is heated toreflux with about one molar equivalent of an alkali metal borate in thealiphatic or alicyclic solvent (e.g. hexane, isohexane, cyclohexane,methylcyclohexane) to form the anilinium borate along with byproductalkali metal chloride, the latter of which can typically be removed byfiltration.

However, it has been unexpectedly discovered that anilinium borateactivators with long-chain aliphatic linear hydrocarbon groups having 6or more carbon atoms can be synthesized in n-hexane and isohexane.Previously, high temperature and cyclic hydrocarbon or polar solventswere necessary for dissolution of anilinium compounds. This synthesisremoves the need to change solvents before addition into the olefinpolymerization process. The yield and purity of the anilinium borateactivator according to the instant disclosure is not changed compared toprevious reaction conditions. The borates used are preferablytetrakis(heptafluoronaphth-2-yl)borate ortetrakis(pentafluorophenyl)borate.

In at least one embodiment, an activator of the present disclosure issoluble in an aliphatic solvent at a concentration of about 1 millimoleper liter or greater, such as about 5 millimole per liter or greater,such as about 10 millimole per liter or greater, such as about 20millimole per liter or greater, such as about 50 millimole per liter orgreater, such as about 100 millimole per liter or greater, such as about200 millimoles per liter or greater, such as about 500 50 millimoles perliter or greater. In at least one embodiment, an activator of thepresent disclosure dissolves in hexane, isohexane, cyclohexane, ormethylcyclohexane at 25° C. to form a homogeneous (i.e., a clear)solution having a concentration of at least 1 millmole per liter, or 5,or 10, or 20, or 50, or 100 millimoles per liter at 25° C.

In at least one embodiment, an activator of the present disclosure issoluble in an aliphatic solvent at a concentration of about 0.1 wt % orgreater, such as about 0.5 wt %, or greater, such as about 1 wt % orgreater, such as about 3 wt % or greater, such as about 5 wt % orgreater, such as about 10 wt % or greater, based on the total weight ofthe activator and the solvent present. In at least one embodiment, anactivator of the present disclosure dissolves in an aliphatic and/oralicyclic solvent of hexane, isohexane, cyclohexane, ormethylcyclohexane at 25° C. to form a clear homogeneous solution havinga concentration of at least 0.1 wt %, or 0.5, or 1, or 3, or 5, or 10 wt% at 25° C. In at least one embodiment, the solubility of the borate oraluminate activators of the present disclosure in aliphatic hydrocarbonsolvents increases with the number of aliphatic carbons in the cationgroup (i.e., the anilinium). In at least one embodiment, a solubility ofat least 10 wt % is achieved with an activator having an anilinium groupof about 21 aliphatic carbon atoms or more, such as about 25 aliphaticcarbons atoms or more, such as about 35 carbon atoms or more.

In at least one embodiment, the solubility of the anilinium borateactivators of the present disclosure in aliphatic hydrocarbon solventsincreases with the number of aliphatic carbons in the anilinium group.In at least one embodiment, a solubility of at least 1 millimole perliter in hexane, isohexane, cyclohexane, or methylcyclohexane at 25° C.is achieved with an activator having an anilinium group of about 21aliphatic carbon atoms or more, such as about 25 aliphatic carbons atomsor more, such as about 35 carbon atoms or more.

Useful aliphatic hydrocarbon solvents for purposes herein includeisobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In at least one embodiment,aromatic entities are present in the solvent, if at all, at less than 1wt %, such as less than 0.5 wt %, such as at 0.01 wt % or less basedupon the total weight of the solvent. The activators of the presentdisclosure can be dissolved in one or more additional solvents.Additional solvents include mixtures comprising ethers, halogenatedhydrocarbon solvents, N,N-dimethylformamide solvents, and combinationsthereof. Preferably the solvents have less than 10 ppm water.

In at least one embodiment, the aliphatic solvent is hexane orisohexane. Accordingly, in embodiments a compound according to formula(A), which is the anilinium halide, is contacted with a compound havingthe general formula M-(BR⁴R⁵R⁶R⁷) in an aliphatic hydrocarbon solvent,an alicyclic hydrocarbon solvent or a combination thereof, at a reactiontemperature and for a period of time sufficient to produce a mixturecomprising the activator compound according to formula (I) and a salthaving the formula M(X); wherein formula (A) is represented by:

wherein formula (I) is represented by:

wherein in each of formulae: each of R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹²is independently a hydrogen or a C₁-C₄₀ linear alkyl; R¹, R², R⁸, R⁹,R¹⁰, R¹¹, and R¹² together comprise 15 or more carbon atoms; each of R⁴,R⁵, R⁶, and R⁷ comprises an aromatic hydrocarbon having from 6 to 24carbon atoms; at least one of R⁴, R⁵, R⁶, and R⁷ is substituted with oneor more fluorine atoms; X is halogen, preferably chlorine or bromine;and M is a Group 1 metal, preferably lithium or sodium.

The process may further comprise filtering or otherwise removing thesalt to produce a clear homogeneous solution comprising the activatorcompound according to formula (I). A portion of the solvent may also beremoved. Preferably the reaction temperature is less than or equal tothe reflux temperature of the solvent at atmospheric pressure, i.e.,less than 101° C., or 81° C., or 68° C., or 60° C. for methylcyclohexane, cyclohexane, hexane and isohexane, respectively.Preferably, the reaction temperature is less than or equal to about 50°C., or 45° C., or 40° C., or 35° C., or 30° C., with room temperature ofabout 25° C. or 20° C., or less being most preferred.

In embodiments, the reaction time is preferably less than or equal toabout 24 hours, with less than 12 hours, or less than 5 hours, or lessthan 3 hours, or less than or equal to about 2 hours, or less than 1hour being most preferred. Suitable conditions may further includeagitation via mechanical or other forms of mixing during the process.

In one or more embodiments, the reaction temperature is from about 20°C. to less than or equal to about 50° C., and the reaction time is lessthan or equal to about 2 hours.

In embodiments, a process of polymerizing olefins to produce at leastone polyolefin comprises contacting at least one olefin with thecatalyst system comprising an activator according to one or moreembodiments disclosed herein. In embodiments, the polymerization processmay further include a scavenger and/or co-activator.

Optional Scavengers or Co-Activators

In addition to the activator compounds disclosed herein, scavengers orco-activators may be used. Aluminum alkyl or organoaluminum compoundswhich may be utilized as scavengers or co-activators include, forexample, trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc.

In at least one embodiment, little or no scavenger is used in theprocess to produce the ethylene polymer. Scavenger (such as trialkylaluminum) can be present at zero mol %, alternately the scavenger ispresent at a molar ratio of scavenger metal to transition metal of lessthan 100:1, such as less than 50:1, such as less than 15:1, such as lessthan 10:1.

Transition Metal Catalyst Compounds

A catalyst system according to the instant disclosure may include one ormore activators according to embodiments disclosed herein and one ormore transition metal compound capable of catalyzing a reaction, such asa polymerization reaction, upon activation with an activator which issuitable for use in polymerization processes of the present disclosure.Transition metal compounds known as metallocenes are exemplary catalystcompounds according to the present disclosure.

In at least one embodiment, the present disclosure provides a catalystsystem comprising a catalyst compound having a metal atom. The catalystcompound can be a metallocene catalyst compound. The metal can be aGroup 3 through Group 12 metal atom, such as Group 3 through Group 10metal atoms, or lanthanide Group atoms. The catalyst compound having aGroup 3 through Group 12 metal atom can be monodentate or multidentate,such as bidentate, tridentate, or tetradentate, where a heteroatom ofthe catalyst, such as phosphorous, oxygen, nitrogen, or sulfur ischelated to the metal atom of the catalyst. Non-limiting examplesinclude bis(phenolate)s. In at least one embodiment, the Group 3 throughGroup 12 metal atom is selected from Group 5, Group 6, Group 8, or Group10 metal atoms. In at least one embodiment, a Group 3 through Group 10metal atom is selected from Cr, Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe,Ru, Os, Co, Rh, Ir, and Ni. In at least one embodiment, a metal atom isselected from Groups 4, 5, and 6 metal atoms. In at least oneembodiment, a metal atom is a Group 4 metal atom selected from Ti, Zr,or Hf. The oxidation state of the metal atom can range from 0 to +7, forexample +1, +2, +3, +4, or +5, for example +2, +3, or +4.

Metallocene Catalyst Compounds

A “metallocene” catalyst compound is preferably a transition metalcatalyst compound having one, two or three, typically one or two,substituted or unsubstituted cyclopentadienyl ligands (such assubstituted or unsubstituted Cp, Ind or Flu) bound to the transitionmetal. Metallocene catalyst compounds as used herein includemetallocenes comprising Group 3 to Group 12 metal complexes, such as,Group 4 to Group 6 metal complexes, for example, Group 4 metalcomplexes. The metallocene catalyst compound of catalyst systems of thepresent disclosure may be unbridged metallocene catalyst compoundsrepresented by the formula: Cp^(A)Cp^(B)M′X′_(n), wherein each Cp^(A)and Cp^(B) is independently selected from cyclopentadienyl ligands (forexample, Cp, Ind, or Flu) and ligands isolobal to cyclopentadienyl, oneor both Cp^(A) and Cp^(B) may contain heteroatoms, and one or bothCp^(A) and Cp^(B) may be substituted by one or more R¹¹ groups; M′ isselected from Groups 3 through 12 atoms and lanthanide Group atoms; X′is an anionic leaving group; n is 0 or an integer from 1 to 4; each R¹¹is independently selected from alkyl, substituted alkyl, heteroalkyl,alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, substitutedalkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio, arylthio, aryl,substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene,haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle,heteroaryl, a heteroatom-containing group, hydrocarbyl, substitutedhydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino, phosphine,amino, amine, ether, and thioether.

In at least one embodiment, each Cp^(A) and Cp^(B) is independentlyselected from cyclopentadienyl, indenyl, fluorenyl, indacenyl,tetrahydroindenyl, cyclopentaphenanthreneyl, benzindenyl, fluorenyl,octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene,phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl,8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl,indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl,hydrogenated and substituted versions thereof. Each Cp^(A) and Cp^(B)may independently be indacenyl or tetrahydroindenyl.

The metallocene catalyst compound may be a bridged metallocene catalystcompound represented by the formula: Cp^(A)(T)Cp^(B)M′X′_(n), whereineach Cp^(A) and Cp^(B) is independently selected from cyclopentadienylligands (for example, Cp, Ind, or Flu) and ligands isolobal tocyclopentadienyl, where one or both Cp^(A) and Cp^(B) may containheteroatoms, and one or both Cp^(A) and Cp^(B) may be substituted by oneor more R¹¹ groups; M′ is selected from Groups 3 through 12 atoms andlanthanide Group atoms, preferably Group 4; X′ is an anionic leavinggroup; n is 0 or an integer from 1 to 4; (T) is a bridging groupselected from divalent alkyl, divalent substituted alkyl, divalentheteroalkyl, divalent alkenyl, divalent substituted alkenyl, divalentheteroalkenyl, divalent alkynyl, divalent substituted alkynyl, divalentheteroalkynyl, divalent alkoxy, divalent aryloxy, divalent alkylthio,divalent arylthio, divalent aryl, divalent substituted aryl, divalentheteroaryl, divalent aralkyl, divalent aralkylene, divalent alkaryl,divalent alkarylene, divalent haloalkyl, divalent haloalkenyl, divalenthaloalkynyl, divalent heteroalkyl, divalent heterocycle, divalentheteroaryl, a divalent heteroatom-containing group, divalenthydrocarbyl, divalent substituted hydrocarbyl, divalentheterohydrocarbyl, divalent silyl, divalent boryl, divalent phosphino,divalent phosphine, divalent amino, divalent amine, divalent ether,divalent thioether. R¹¹ is selected from alkyl, substituted alkyl,heteroalkyl, alkenyl, substituted alkenyl, heteroalkenyl, alkynyl,substituted alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio,arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene,alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl,heterocycle, heteroaryl, a heteroatom-containing group, hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino,phosphine, amino, amine, germanium, ether, and thioether.

In at least one embodiment, each of Cp^(A) and Cp^(B) is independentlyselected from cyclopentadienyl, indenyl, fluorenyl,cyclopentaphenanthreneyl, benzindenyl, fluorenyl, octahydrofluorenyl,cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl,3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl,7-H-dibenzofluorenyl, indeno[1,2-9]anthrene, thiophenoindenyl,thiophenofluorenyl, hydrogenated, and substituted versions thereof,preferably cyclopentadienyl, n-propylcyclopentadienyl, indenyl,pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, andn-butylcyclopentadienyl. Each Cp^(A) and Cp^(B) may independently beindacenyl or tetrahydroindenyl.

(T) is a bridging group containing at least one Group 13, 14, 15, or 16element, in particular boron or a Group 14, 15 or 16 element, preferably(T) is O, S, NR′, or SiR′₂, where each R′ is independently hydrogen orC₁-C₂₀ hydrocarbyl.

In another embodiment, the metallocene catalyst compound is representedby the formula:T _(y) Cp _(m) MG _(n) X _(q)where Cp is independently a substituted or unsubstitutedcyclopentadienyl ligand (for example, substituted or unsubstituted Cp,Ind, or Flu) or substituted or unsubstituted ligand isolobal tocyclopentadienyl; M is a Group 4 transition metal; G is a heteroatomgroup represented by the formula JR*z where J is N, P, O or S, and R* isa linear, branched, or cyclic C₁-C₂₀ hydrocarbyl; z is 1 or 2; T is abridging group; y is 0 or 1; X is a leaving group; m=1, n=1, 2 or 3,q=0, 1, 2 or 3, and the sum of m+n+q is equal to the coordination numberof the transition metal.

In at least one embodiment, J is N, and R* is methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl,decyl, undecyl, dodecyl, adamantyl or an isomer thereof.

In at least one embodiment, the catalyst compound is represented byformula (II) or formula (III):

wherein in each of formula (II) and formula (III):

M is the metal center, and is a Group 4 metal, such as titanium,zirconium or hafnium, such as zirconium or hafnium when L₁ and L₂ arepresent and titanium when Z is present;

n is 0 or 1;

T is an optional bridging group which, if present, is a bridging groupcontaining at least one Group 13, 14, 15, or 16 element, in particularboron or a Group 14, 15 or 16 element (preferably T is selected fromdialkylsilyl, diarylsilyl, dialkylmethyl, ethylenyl (—CH₂—CH₂—) orhydrocarbylethylenyl wherein one, two, three or four of the hydrogenatoms in ethylenyl are substituted by hydrocarbyl, where hydrocarbyl canbe independently C₁ to C alkyl or phenyl, tolyl, xylyl and the like),and when T is present, the catalyst represented can be in a racemic or ameso form;

L₁ and L₂ are independently cyclopentadienyl, indenyl, tetrahydroindenylor fluorenyl, optionally substituted, that are each bonded to M, or L₁and L₂ are independently cyclopentadienyl indenyl, tetrahydroindenyl orfluorenyl, which are optionally substituted, in which any two adjacentsubstituents on L¹ and L² are optionally joined to form a substituted orunsubstituted, saturated, partially unsaturated, or aromatic cyclic orpolycyclic substituent;

Z is nitrogen, oxygen, sulfur, or phosphorus; q is 1 or 2; R′ is acyclic, linear or branched C₁ to C₁₀ alkyl or substituted alkyl group(such as Z—R′ form a cyclododecylamido group):

X₁ and X₂ are, independently, hydrogen, halogen, hydride radicals,hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbylradicals, substituted halocarbyl radicals, silylcarbyl radicals,substituted silylcarbyl radicals, germylcarbyl radicals, or substitutedgermylcarbyl radicals; or X₁ and X₂ are joined and bound to the metalatom to form a metallacycle ring containing from about 3 to about 20carbon atoms; or both together can be an olefin, diolefin or aryneligand.

Preferably, T in any formula herein is present and is a bridging groupcontaining at least one Group 13, 14, 15, or 16 element, in particular aGroup 14 element. Examples of suitable bridging groups include P(═S)R′,P(═Se)R′, P(═O)R′, R′₂C, R′₂Si, R′₂Ge, R′₂CCR′₂, R′₂CCR′₂CR′₂,R′₂CCR′₂CR′₂CR′₂, R′C═CR′, R′C═CR′CR′₂, R′₂CCR′═CR′CR′₂, R′C═CR′CR′═CR′,R′C═CR′CR′₂CR′₂, R′₂CSiR′₂, R′₂SiSiR′₂, R′₂SiOSiR′₂, R′₂CSiR′₂CR′₂,R′₂SiCR′₂SiR′₂, R′C═CR′SiR′₂, R′₂CGeR′₂, R′₂GeGeR′₂, R′₂CGeR′₂CR′₂,R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂, R′C═CR′GeR′₂, R′B, R′₂C—BR′, R′₂C—BR′—CR′₂,R′₂C—O—CR′₂, R′₂CR′₂C—O—CR′₂CR′₂, R′₂C—O—CR′₂CR′₂, R′₂C—O—CR′═CR′,R′₂C—S—CR′₂, R′₂CR′₂C—S—CR′₂CR′₂, R′₂C—S—CR′₂CR′₂, R′₂C—S—CR′═CR′,R′₂C—Se—CR′₂, R′₂CR′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′═CR′,R′₂C—N═CR′, R′₂C—NR′—CR′₂, R′₂C—NR′—CR′₂CR′₂, R′₂C—NR′—CR′═CR′,R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′, R′₂C—PR′—CR′₂, O, S, Se, Te, NR′,PR′, AsR′, SbR′, O—O, S—S, R′N—NR′, R′P—PR′, O—S, O—NR′, O—PR′, S—NR′,S—PR′, and R′N—PR′ where R′ is hydrogen or a C₁-C₂₀ containinghydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl or germylcarbyl substituent and optionally twoor more adjacent R′ may join to form a substituted or unsubstituted,saturated, partially unsaturated or aromatic, cyclic or polycyclicsubstituent. Preferred examples for the bridging group T include CH₂,CH₂CH₂, SiMe₂, SiPh₂, SiMePh, Si(CH₂)₃, Si(CH₂)₄, O, S, NPh, PPh, NMe,PMe, NEt, NPr, NBu, PEt, PPr, Me₂SiOSiMe₂, and PBu.

In a preferred embodiment of the invention in any embodiment of anyformula described herein, T is represented by the formula R^(a) ₂J or(R^(a) ₂J)₂, where J is C, Si, or Ge, and each R^(a) is, independently,hydrogen, halogen, C₁ to C₂₀ hydrocarbyl (such as methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl)or a C₁ to C₂₀ substituted hydrocarbyl, and two R^(a) can form a cyclicstructure including aromatic, partially saturated, or saturated cyclicor fused ring system. Preferably, T is a bridging group comprisingcarbon or silica, such as dialkylsilyl, preferably T is selected fromCH₂, CH₂CH₂, C(CH₃)₂, SiMe₂, SiPh₂, SiMePh, silylcyclobutyl (Si(CH₂)₃),(Ph)₂C, (p-(Et)₃SiPh)₂C, Me₂SiOSiMe₂, and cyclopentasilylene (Si(CH₂)₄).

In at least one embodiment, the catalyst compound has a symmetry that isC₂ symmetrical.

The metallocene catalyst component may comprise any combination of any“embodiment” described herein.

Suitable metallocenes useful herein include, but are not limited to, themetallocenes disclosed and referenced in the US patents cited above, aswell as those disclosed and referenced in U.S. Pat. Nos. 7,179,876;7,169,864; 7,157,531; 7,129,302; 6,995,109; 6,958,306; 6,884,748;6,689,847; US Patent publication 2007/0055028, and published PCTApplications WO 97/22635; WO 00/699/22; WO 01/30860; WO 01/30861; WO02/46246; WO 02/50088; WO 04/026921; and WO 06/019494, all fullyincorporated herein by reference. Additional catalysts suitable for useherein include those referenced in U.S. Pat. Nos. 6,309,997; 6,265,338;US Patent publication 2006/019925, and the following articles: Resconi,L. et al. (2000) “Selectivity in Propene Polymerization with MetalloceneCatalysts,” Chem. Rev., v. 100, pp. 1253-1345; Gibson, V. C. et al.(2003) “Advances in Non-Metallocene Olefin Polymerization Catalysis,”Chem. Rev., v. 103, pp. 283-315; Nakayama, Y. et al. (2006)“MgCl₂/R′_(n)Al(OR)_(3-n): An Excellent Activator/Support forTransition-Metal Complexes for Olefin Polymerization,” Chem. Eur. J., v12(29), pp. 7546-7556; Nakayama, Y. et al. (2004) “Olefin PolymerizationBehavior of bis(phenoxy-imine) Zr, Ti, and V Complexes with MgCl₂-BasedCocatalysts,” J. Molecular Catalysis A: Chemical, v. 213(1), pp.141-150; Nakayama, Y. et al. (2005) “Propylene Polymerization Behaviorof Fluorinated Bis(phenoxy-imine) Ti Complexes with an MgCl₂—BasedCompound (MgCl₂—Supported Ti-Based Catalysts),” Macromol. Chem. Phys.,v. 206(18), pp. 1847-1852; and Matsui, S. et al. (2001) “A Family ofZirconium Complexes having Two Phenoxy-Imine Chelate Ligands for OlefinPolymerization,” J. Am. Chem. Soc., v. 123(28), pp. 6847-6856.

Exemplary metallocene compounds useful herein include:

-   bis(cyclopentadienyl)zirconium dichloride,-   bis(n-butylcyclopentadienyl)zirconium dichloride,-   bis(n-butylcyclopentadienyl)zirconium dimethyl,-   bis(pentamethylcyclopentadienyl)zirconium dichloride,-   bis(pentamethylcyclopentadienyl)zirconium dimethyl,-   bis(pentamethylcyclopentadienyl)hafnium dichloride,-   bis(pentamethylcyclopentadienyl)zirconium dimethyl,-   bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride,-   bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,-   bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride,-   bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,-   bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dimethyl,-   bis(tetrahydro-1-indenyl)zirconium dichloride,-   bis(tetrahydro-1-indenyl)zirconium dimethyl,-   (n-propyl cyclopentadienyl, pentamethyl cyclopentadienyl)zirconium    dichloride, and-   (n-propyl cyclopentadienyl, pentamethyl cyclopentadienyl)zirconium    dimethyl.

In at least one embodiment, the catalyst compound may be selected from:

-   dimethylsilylbis(tetrahydroindenyl)MX_(n),-   dimethylsilyl bis(2-methylindenyl)MX_(n),-   dimethylsilyl bis(2-methylfluorenyl)MX_(n),-   dimethylsilyl bis(2-methyl-5,7-propylindenyl)MX_(n),-   dimethylsilyl bis(2-methyl-4-phenylindenyl)MX_(n),-   dimethylsilyl bis(2-ethyl-5-phenylindenyl)MX_(n),-   dimethylsilyl bis(2-methyl-4-biphenylindenyl)MX_(n),-   dimethylsilylene bis(2-methyl-4-carbazolylindenyl)MX_(n),-   rac-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz(f)indene)MX_(n),-   diphenylmethylene (cyclopentadienyl)(fluoreneyl)MX_(n),-   bis(methylcyclopentadienyl)MX_(n),-   rac-dimethylsiylbis(2-methyl,3-propyl indenyl)MX_(n),-   dimethylsilylbis(indenyl)MX_(n),-   Rac-meso-diphenylsilyl-bis(n-propylcyclopentadienyl)MX_(n),-   1,    1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tertiary-butyl-1-fluorenyl)MX_(n)    (bridge is considered the 1 position),-   bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(di-t-butylfluorenyl)MX_(n),-   bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(fluorenyl)MX_(n),-   bisphenylmethylene(cyclopentadienyl)(dimethylfluorenyl)MX_(n),-   bis(n-propylcyclopentadienyl)MX_(n),-   bis(n-butylcyclopentadienyl)MX_(n),-   bis(n-pentylcyclopentadienyl)MX_(n),-   (n-propyl cyclopentadienyl)(n-butylcyclopentadienyl)MX_(n),-   bis[(2-trimethylsilylethyl)cyclopentadienyl]MX_(n),-   bis(trimethylsilyl cyclopentadienyl)MX_(n),-   dimethylsilylbis(n-propylcyclopentadienyl)MX_(n),-   dimethylsilylbis(n-butylcyclopentadienyl)MX_(n),-   bis(1-n-propyl-2-methylcyclopentadienyl)MX_(n),-   (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)MX_(n),-   bis(1-methyl, 3-n-butyl cyclopentadienyl)MX_(n),-   bis(indenyl)MX_(n),-   dimethylsilyl    (tetramethylcyclopentadienyl)(cyclododecylamido)MX_(n),-   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)MX_(n),-   μ-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)MX_(n),-   μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)MX_(n),-   μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)MX_(n),-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)MX_(n),-   μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)MX_(n),-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)MX_(n),-   μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)MX_(n),-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)MX_(n),-   μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)MX_(n),    and/or-   μ-(CH₃)₂Si(η⁵-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)MX_(n),    where M is selected from Ti, Zr, and Hf; where X is selected from    the group consisting of halogens, hydrides, C₁₋₁₂ alkyls, C₂₋₁₂    alkenyls, C₆₋₁₂ aryls, C₇₋₂₀ alkylaryls, C₁₋₁₂ alkoxys, C₆₋₁₆    aryloxys, C₇₋₁₈ alkylaryloxys, C₁₋₁₂ fluoroalkyls, C₆₋₁₂    fluoroaryls, and C₁₋₁₂ heteroatom-containing hydrocarbons,    substituted derivatives thereof, and combinations thereof, and where    n is zero or an integer from 1 to 4, preferably X is selected from    halogens (such as bromide, fluoride, chloride), or C₁ to C₂₀ alkyls    (such as methyl, ethyl, propyl, butyl, and pentyl) and n is 1 or 2,    preferably 2.

In other embodiments of the invention, the catalyst is one or more of:

-   bis(1-methyl, 3-n-butyl cyclopentadienyl) M(R)₂;-   dimethylsilyl bis(indenyl)M(R)₂;-   bis(indenyl)M(R)₂;-   dimethylsilyl bis(tetrahydroindenyl)M(R)₂;-   bis(n-propylcyclopentadienyl)M(R)₂;-   dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M(R)₂;-   dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M(R)₂;-   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M(R)₂;-   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M(R)₂;-   μ-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)M(R)₂;-   μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M(R)₂;-   μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;-   μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M(R)₂;-   μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)M(R)₂;-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂;-   μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂;-   μ-(CH₃)₂Si(η⁵-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)M(R)₂;    where M is selected from Ti, Zr, and Hf; and R is selected from    halogen or C₁ to C₅ alkyl.

In preferred embodiments of the invention, the catalyst compound is oneor more of:

-   dimethylsilyl    (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl;-   dimethylsilyl    (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl;-   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium    dimethyl;-   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium    dimethyl;-   μ-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)titanium dimethyl;-   μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)titanium    dimethyl;-   μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)titanium    dimethyl;-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)titanium    dimethyl;-   μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)titanium    dimethyl;-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)titanium    dimethyl₂;-   μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)titanium dimethyl;-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)titanium    dimethyl;-   μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)titanium    dimethyl; and/or-   μ-(CH₃)₂Si(η⁵-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)titanium    dimethyl.

In at least one embodiment, the catalyst israc-dimethylsilyl-bis(indenyl)hafnium dimethyl and or 1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tertiary-butyl-1-fluorenyl)hafniumdimethyl.

In at least one embodiment, the catalyst compound is one or more of:

-   bis(1-methyl, 3-n-butyl cyclopentadienyl)hafnium dimethyl,-   bis(1-methyl, 3-n-butyl cyclopentadienyl)zirconium dimethyl,-   dimethylsilyl bis(indenyl)zirconium dimethyl,-   dimethylsilyl bis(indenyl)hafnium dimethyl,-   bis(indenyl)zirconium dimethyl,-   bis(indenyl)hafnium dimethyl,-   dimethylsilyl bis(tetrahydroindenyl)zirconium dimethyl,-   bis(n-propylcyclopentadienyl)zirconium dimethyl,-   dimethylsilylbis(tetrahydroindenyl)hafnium dimethyl,-   dimethylsilyl bis(2-methylindenyl)zirconium dimethyl,-   dimethylsilyl bis(2-methylfluorenyl)zirconium dimethyl,-   dimethylsilyl bis(2-methylindenyl)hafnium dimethyl,-   dimethylsilyl bis(2-methylfluorenyl)hafnium dimethyl,-   dimethylsilyl bis(2-methyl-5,7-propylindenyl) zirconium dimethyl,-   dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl,-   dimethylsilyl bis(2-ethyl-5-phenylindenyl) zirconium dimethyl,-   dimethylsilyl bis(2-methyl-4-biphenylindenyl) zirconium dimethyl,-   dimethylsilylene bis(2-methyl-4-carbazolylindenyl) zirconium    dimethyl,-   rac-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz(f)indene)hafnium    dimethyl,-   diphenylmethylene (cyclopentadienyl)(fluoreneyl)hafnium dimethyl,-   bis(methylcyclopentadienyl)zirconium dimethyl,-   rac-dimethylsiylbis(2-methyl,3-propyl indenyl)hafnium dimethyl,-   dimethylsilylbis(indenyl)hafnium dimethyl,-   dimethylsilylbis(indenyl)zirconium dimethyl,-   dimethyl    rac-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz(f)indene)hafnium    dimethyl,-   Rac-meso-diphenylsilyl-bis(n-propylcyclopentadienyl)hafnium    dimethyl,-   1,    1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tertiary-butyl-1-fluorenyl)hafnium    X_(n) (bridge is considered the 1 position),-   bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(di-t-butylfluorenyl)hafnium    dimethyl,-   bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(fluorenyl)hafnium    dimethyl,-   bisphenylmethylene(cyclopentadienyl)(dimethylfluorenyl)hafnium    dimethyl,-   bis(n-propylcyclopentadienyl)hafnium dimethyl,-   bis(n-butylcyclopentadienyl)hafnium dimethyl,-   bis(n-pentylcyclopentadienyl)hafnium dimethyl,-   (n-propyl cyclopentadienyl)(n-butylcyclopentadienyl)hafnium    dimethyl,-   bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium dimethyl,-   bis(trimethylsilyl cyclopentadienyl)hafnium dimethyl,-   dimethylsilylbis(n-propylcyclopentadienyl)hafnium dimethyl,-   dimethylsilylbis(n-butylcyclopentadienyl)hafnium dimethyl,-   bis(1-n-propyl-2-methylcyclopentadienyl)hafnium dimethyl, and-   (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium    dimethyl,-   bis(n-propylcyclopentadienyl)hafnium dimethyl,-   bis(n-butylcyclopentadienyl)hafnium dimethyl,-   bis(n-pentylcyclopentadienyl)hafnium dimethyl,-   (n-propyl cyclopentadienyl)(n-butylcyclopentadienyl)hafnium    dimethyl,-   bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium dimethyl,-   bis(trimethylsilyl cyclopentadienyl)hafnium dimethyl,-   dimethylsilylbis(n-propylcyclopentadienyl)hafnium dimethyl,-   dimethylsilylbis(n-butylcyclopentadienyl)hafnium dimethyl,-   bis(1-n-propyl-2-methylcyclopentadienyl)hafnium dimethyl,-   (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium    dimethyl, and/or-   dimethylsilyl(3-n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium    dimethyl.    Non-Metallocene Catalyst Compounds

Transition metal complexes for polymerization processes can include anyolefin polymerization catalyst. Suitable catalyst components may include“non-metallocene complexes” that are defined to be transition metalcomplexes that do not feature a cyclopentadienyl anion or substitutedcyclopentadienyl anion donors (e.g., cyclopentadienyl, fluorenyl,indenyl, methylcyclopentadienyl). Examples of families ofnon-metallocene complexes that may be suitable can include latetransition metal pyridylbisimines (e.g., U.S. Pat. No. 7,087,686), group4 pyridyldiamidos (e.g., U.S. Pat. No. 7,973,116), quinolinyldiamidos(e.g., US Pub. No. 2018/0002352 A1), pyridylamidos (e.g., U.S. Pat. No.7,087,690), phenoxyimines (e.g., Makio, H. et al. (2009) “Developmentand Application of FI Catalysts for Olefin Polymerization: UniqueCatalysis and Distinctive Polymer Formation,” Accounts of ChemicalResearch, v. 42(10), pp. 1532-1544), and bridged bi-aromatic complexes(e.g., U.S. Pat. No. 7,091,292), the disclosures of which areincorporated herein by reference.

Catalyst complexes that are suitable for use in combination with theactivators described herein include: pyridyldiamido complexes;quinolinyldiamido complexes; phenoxyimine complexes; bisphenolatecomplexes; cyclopentadienyl-amidinate complexes; and iron pyridylbis(imine) complexes or any combination thereof, including anycombination with metallocene complexes.

The term “pyridyldiamido complex” or “pyridyldiamide complex” or“pyridyldiamido catalyst” or “pyridyldiamide catalyst” refers to a classof coordination complexes described in U.S. Pat. No. 7,973,116B2, US2012/0071616A1, US 2011/0224391A1, US 2011/0301310A1, US 2015/0141601A1,U.S. Pat. Nos. 6,900,321 and 8,592,615 that feature a dianionictridentate ligand that is coordinated to a metal center through oneneutral Lewis basic donor atom (e.g., a pyridine group) and a pair ofanionic amido or phosphido (i.e., deprotonated amine or phosphine)donors. In these complexes the pyridyldiamido ligand is coordinated tothe metal with the formation of one five membered chelate ring and oneseven membered chelate ring. It is possible for additional atoms of thepyridyldiamido ligand to be coordinated to the metal without affectingthe catalyst function upon activation; an example of this could be acyclometalated substituted aryl group that forms an additional bond tothe metal center.

The term “quinolinyldiamido complex” or “quinolinyldiamido catalyst” or“quinolinyldiamide complex” or “quinolinyldiamide catalyst” refers to arelated class of pyridyldiamido complex/catalyst described in US2018/0002352 where a quinolinyl moiety is present instead of a pyridylmoiety.

The term “phenoxyimine complex” or “phenoxyimine catalyst” refers to aclass of coordination complexes described in EP 0874005 that feature amonoanionic bidentate ligand that is coordinated to a metal centerthrough one neutral Lewis basic donor atom (e.g., an imine moiety) andan anionic aryloxy (i.e., deprotonated phenoxy) donor. Typically, two ofthese bidentate phenoxyimine ligands are coordinated to a group 4 metalto form a complex that is useful as a catalyst component.

The term “bisphenolate complex” or “bisphenolate catalyst” refers to aclass of coordination complexes described in U.S. Pat. No. 6,841,502, WO2017/004462, and WO 2006/020624 that feature a dianionic tetradentateligand that is coordinated to a metal center through two neutral Lewisbasic donor atoms (e.g., oxygen bridge moieties) and two anionic aryloxy(i.e., deprotonated phenoxy) donors.

The term “cyclopentadienyl-amidinate complex” or“cyclopentadienyl-amidinate catalyst” refers to a class of coordinationcomplexes described in U.S. Pat. No. 8,188,200 that typically feature agroup 4 metal bound to a cyclopentadienyl anion, a bidentate amidinateanion, and a couple of other anionic groups.

The term “iron pyridyl bis(imine) complex” refers to a class of ironcoordination complexes described in U.S. Pat. No. 7,087,686 thattypically feature an iron metal center coordinated to a neutral,tridentate pyridyl bis(imine) ligand and two other anionic ligands.

Non-metallocene complexes can include iron complexes of tridentatepyridylbisimine ligands, zirconium and hafnium complexes of pyridylamidoligands, zirconium and hafnium complexes of tridentate pyridyldiamidoligands, zirconium and hafnium complexes of tridentate quinolinyldiamidoligands, zirconium and hafnium complexes of bidentate phenoxyimineligands, and zirconium and hafnium complexes of bridged bi-aromaticligands.

Suitable non-metallocene complexes can include zirconium and hafniumnon-metallocene complexes. In at least one embodiment, non-metallocenecomplexes for the present disclosure include group 4 non-metallocenecomplexes including two anionic donor atoms and one or two neutral donoratoms. Suitable non-metallocene complexes for the present disclosureinclude group 4 non-metallocene complexes including an anionic amidodonor. Suitable non-metallocene complexes for the present disclosureinclude group 4 non-metallocene complexes including an anionic aryloxidedonor atom. Suitable non-metallocene complexes for the presentdisclosure include group 4 non-metallocene complexes including twoanionic aryloxide donor atoms and two additional neutral donor atoms.

A catalyst compounds can be a quinolinyldiamido (QDA) transition metalcomplex represented by formula (BI), such as by formula (BII), such asby formula (BIII):

wherein:

M is a group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal, such as a group 4metal;

J is group including a three-atom-length bridge between the quinolineand the amido nitrogen, such as a group containing up to 50 non-hydrogenatoms;

E is carbon, silicon, or germanium;

X is an anionic leaving group, (such as a hydrocarbyl group or ahalogen);

L is a neutral Lewis base;

R¹ and R¹³ are independently selected from the group including ofhydrocarbyls, substituted hydrocarbyls, and silyl groups;

R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R^(10′), R¹¹, R^(11′), R¹², and R¹⁴are independently hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy,substituted hydrocarbyl, halogen, or phosphino;

n is 1 or 2;

m is 0, 1, or 2, where

n+m is not greater than 4; and

any two R groups (e.g., R¹ & R², R² & R³, R¹⁰ and R¹¹, etc.) may bejoined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl,substituted heterocyclic, or unsubstituted heterocyclic, saturated orunsaturated ring, where the ring has 5, 6, 7, or 8 ring atoms and wheresubstitutions on the ring can join to form additional rings;

any two X groups may be joined together to form a dianionic group;

any two L groups may be joined together to form a bidentate Lewis base;and

any X group may be joined to an L group to form a monoanionic bidentategroup.

In at least one embodiment, M is a group 4 metal, such as zirconium orhafnium, such as M is hafnium.

Representative non-metallocene transition metal compounds usable forforming poly(alpha-olefin)s of the present disclosure also includetetrabenzyl zirconium, tetra bis(trimethylsilymethyl) zirconium,oxotris(trimethlsilylmethyl) vanadium, tetrabenzyl hafnium, tetrabenzyltitanium, bis(hexamethyl disilazido)dimethyl titanium, tris(trimethylsilyl methyl) niobium dichloride, and tris(trimethylsilylmethyl)tantalum dichloride.

In at least one embodiment, J is an aromatic substituted orunsubstituted hydrocarbyl having from 3 to 30 non-hydrogen atoms, suchas J is represented by the formula:

such as J is

where R⁷, R⁸, R⁹, R¹⁰, R^(10′), R¹¹, R^(11′), R¹², R¹⁴ and E are asdefined above, and any two R groups (e.g., R⁷ & R⁸, R⁸ & R⁹, R⁹ & R¹⁰,R¹⁰ & R¹¹, etc.) may be joined to form a substituted or unsubstitutedhydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ringatoms (such as 5 or 6 atoms), and said ring may be saturated orunsaturated (such as partially unsaturated or aromatic), such as J is anarylalkyl (such as arylmethyl, etc.) or dihydro-1H-indenyl, ortetrahydronaphthalenyl group.

In at least one embodiment, J is selected from the following structures:

where

indicates connection to the complex.

In at least one embodiment, E is carbon.

X may be an alkyl (such as alkyl groups having 1 to 10 carbons, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, and isomers thereof), aryl, hydride, alkylsilane, fluoride,chloride, bromide, iodide, triflate, carboxylate, amido (such as NMe₂),or alkylsulfonate.

In at least one embodiment, L is an ether, amine or thioether.

In at least one embodiment, R⁷ and R⁸ are joined to form a six-memberedaromatic ring with the joined R⁷/R⁸ group being —CH═CHCH═CH—.

R¹⁰ and R¹¹ may be joined to form a five-membered ring with the joinedR¹⁰R¹¹ group being —CH₂CH₂—.

In at least one embodiment, R¹⁰ and R¹¹ are joined to form asix-membered ring with the joined R¹⁰R¹¹ group being —CH₂CH₂CH₂—.

R¹ and R¹³ may be independently selected from phenyl groups that arevariously substituted with between zero to five substituents thatinclude F, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino, aryl, and alkylgroups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.

In at least one embodiment, the QDA transition metal complex representedby the formula (BII) above where:

M is a group 4 metal (such hafnium);

E is selected from carbon, silicon, or germanium (such as carbon);

X is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide,iodide, triflate, carboxylate, amido, alkoxo, or alkylsulfonate;

L is an ether, amine, or thioether;

R¹ and R¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups (such as aryl);

R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independentlyhydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substitutedhydrocarbyls, halogen, and phosphino;

n is 1 or 2;

m is 0, 1, or 2;

n+m is from 1 to 4;

two X groups may be joined together to form a dianionic group;

two L groups may be joined together to form a bidentate Lewis base;

an X group may be joined to an L group to form a monoanionic bidentategroup;

R⁷ and R⁸ may be joined to form a ring (such as an aromatic ring, asix-membered aromatic ring with the joined R⁷R⁸ group being—CH═CHCH═CH—); and

R¹⁰ and R¹¹ may be joined to form a ring, such as a five-membered ringwith the joined R¹⁰R¹¹ group being —CH₂CH₂—, a six-membered ring withthe joined R¹⁰R¹¹ group being —CH₂CH₂CH₂.

In at least one embodiment of formula (BI), (BII), and (BIII), R⁴, R⁵,and R⁶ are independently selected from the group including hydrogen,hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino,and silyl, and wherein adjacent R groups (R⁴ and R⁵ and/or R⁵ and R⁶)are joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl,unsubstituted heterocyclic ring or substituted heterocyclic ring, wherethe ring has 5, 6, 7, or 8 ring atoms and where substitutions on thering can join to form additional rings.

In at least one embodiment of formula (BI), (BII), and (BIII), R⁷, R⁸,R⁹, and R¹⁰ are independently selected from the group includinghydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen,amino, and silyl, and wherein adjacent R groups (R⁷ and R⁸ and/or R⁹ andR¹⁰) may be joined to form a saturated, substituted hydrocarbyl,unsubstituted hydrocarbyl, unsubstituted heterocyclic ring orsubstituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ringcarbon atoms and where substitutions on the ring can join to formadditional rings.

In at least one embodiment of formula (BI), (BII), and (BIII), R² and R³are each, independently, selected from the group including hydrogen,hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino,aryloxy, halogen, and phosphino, R² and R³ may be joined to form asaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ringcan join to form additional rings, or R² and R³ may be joined to form asaturated heterocyclic ring, or a saturated substituted heterocyclicring where substitutions on the ring can join to form additional rings.

In at least one embodiment of formula (BI), (BII), and (BIII), R¹¹ andR¹² are each, independently, selected from the group including hydrogen,hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino,aryloxy, halogen, and phosphino, R¹¹ and R¹² may be joined to form asaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ringcan join to form additional rings, or R¹¹ and R¹² may be joined to forma saturated heterocyclic ring, or a saturated substituted heterocyclicring where substitutions on the ring can join to form additional rings,or R¹¹ and R¹⁰ may be joined to form a saturated heterocyclic ring, or asaturated substituted heterocyclic ring where substitutions on the ringcan join to form additional rings.

In at least one embodiment of formula (BI), (BII), and (BIII), R¹ andR¹³ are independently selected from phenyl groups that are variouslysubstituted with between zero to five substituents that include F, Cl,Br, I, CF₃, NO₂, alkoxy, dialkylamino, aryl, and alkyl groups having 1to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, and isomers thereof.

In at least one embodiment of formula (BII), suitable R¹²-E-R¹¹ groupsinclude CH₂, CMe₂, SiMe₂, SiEt₂, SiPr₂, SiBu₂, SiPh₂, Si(aryl)₂,Si(alkyl)₂, CH(aryl), CH(Ph), CH(alkyl), and CH(2-isopropylphenyl),where alkyl is a C₁ to C₄₀ alkyl group (such as C₁ to C₂₀ alkyl, such asone or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof), aryl is aC₅ to C₄₀ aryl group (such as a C₆ to C₂₀ aryl group, such as phenyl orsubstituted phenyl, such as phenyl, 2-isopropylphenyl, or2-tertbutylphenyl).

In at least one embodiment of formula (BIII), R¹¹, R¹², R⁹, R¹⁴, and R¹⁰are independently selected from the group consisting of hydrogen,hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, andsilyl, and wherein adjacent R groups (R¹⁰ and R¹⁴, and/or R¹¹ and R¹⁴,and/or R⁹ and R¹⁰) may be joined to form a saturated, substitutedhydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ringor substituted heterocyclic ring, where the ring has 5, 6, 7, or 8 ringcarbon atoms and where substitutions on the ring can join to formadditional rings.

The R groups above (i.e., any of R² to R¹⁴) and other R groups mentionedhereafter may contain from 1 to 30, such as 2 to 20 carbon atoms, suchas from 6 to 20 carbon atoms. The R groups above (i.e., any of R² toR¹⁴) and other R groups mentioned hereafter, may be independentlyselected from the group including hydrogen, methyl, ethyl, phenyl,isopropyl, isobutyl, trimethylsilyl, and —CH₂—Si(Me)₃.

In at least one embodiment, the quinolinyldiamide complex is linked toone or more additional transition metal complex, such as aquinolinyldiamide complex or another suitable non-metallocene, throughan R group in such a fashion as to make a bimetallic, trimetallic, ormultimetallic complex that may be used as a catalyst component forolefin polymerization. The linker R-group in such a complex may contain1 to 30 carbon atoms.

In at least one embodiment, E is carbon and R¹¹ and R¹² areindependently selected from phenyl groups that are substituted with 0,1, 2, 3, 4, or 5 substituents selected from the group consisting of F,Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino, hydrocarbyl, and substitutedhydrocarbyl groups with from one to ten carbons.

In at least one embodiment of formula (BII) or (BIII), R¹¹ and R¹² areindependently selected from hydrogen, methyl, ethyl, phenyl, isopropyl,isobutyl, —CH₂—Si(Me)₃, and trimethylsilyl.

In at least one embodiment of formula (BII), and (BIII), R⁷, R⁸, R⁹, andR¹⁰ are independently selected from hydrogen, methyl, ethyl, propyl,isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy,—CH₂—Si(Me)₃, and trimethylsilyl.

In at least one embodiment of formula (BI), (BII), and (BIII), R², R³,R⁴, R⁵, and R⁶ are independently selected from the group consisting ofhydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls,and halogen.

In at least one embodiment of formula (BIII), R¹⁰, R¹¹ and R¹⁴ areindependently selected from hydrogen, methyl, ethyl, phenyl, isopropyl,isobutyl, —CH₂—Si(Me)₃, and trimethylsilyl.

In at least one embodiment of formula (BI), (BII), and (BIII), each L isindependently selected from Et₂O, MeOtBu, Et₃N, PhNMe₂, MePh₂N,tetrahydrofuran, and dimethylsulfide.

In at least one embodiment of formula (BI), (BII), and (BIII), each X isindependently selected from methyl, benzyl, trimethylsilyl, neopentyl,ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo,dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

In at least one embodiment of formula (BI), (BII), and (BIII), R¹ is2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl,2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl,2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl,2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl.

In at least one embodiment of formula (BI), (BII), and (BIII), R¹³ isphenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl,2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl,3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl,3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.

In at least one embodiment of formula (BII), J is dihydro-1H-indenyl andR¹ is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.

In at least one embodiment of formula (BI), (BII), and (BIII), R¹ is2,6-diisopropylphenyl and R¹³ is a hydrocarbyl group containing 1, 2, 3,4, 5, 6, or 7 carbon atoms.

An exemplary catalyst used for polymerizations of the present disclosureis (QDA-1)HfMe₂, as described in US Pub. No. 2018/0002352 A1.

In at least one embodiment, the catalyst compound is a bis(phenolate)catalyst compound represented by formula (CI):

M is a Group 4 metal, such as Hf or Zr. X¹ and X² are independently aunivalent C₁-C₂₀ hydrocarbyl, C₁-C₂₀ substituted hydrocarbyl, aheteroatom or a heteroatom-containing group, or X¹ and X² join togetherto form a C₄-C₆₂ cyclic or polycyclic ring structure. R¹, R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independently hydrogen, C₁-C₄₀hydrocarbyl, C₁-C₄₀ substituted hydrocarbyl, a heteroatom or aheteroatom-containing group, or two or more of R¹, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, or R¹⁰ are joined together to form a C₄-C₆₂ cyclic orpolycyclic ring structure, or a combination thereof; Q is a neutraldonor group; J is heterocycle, a substituted or unsubstituted C₇-C₆₀fused polycyclic group, where at least one ring is aromatic and where atleast one ring, which may or may not be aromatic, has at least five ringatoms' G is as defined for J or may be hydrogen, C₂-C₆₀ hydrocarbyl,C₁-C₆₀ substituted hydrocarbyl, or may independently form a C₄-C₆₀cyclic or polycyclic ring structure with R⁶, R⁷, or R⁸ or a combinationthereof; Y is divalent C₁-C₂₀ hydrocarbyl or divalent C₁-C₂₀ substitutedhydrocarbyl or (-Q*-Y—) together form a heterocycle; and heterocycle maybe aromatic and/or may have multiple fused rings.

In at least one embodiment, the catalyst compound represented by formula(CI) is represented by formula (CII) or formula (CIII):

M is Hf, Zr, or Ti. X¹, X², R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, andY are as defined for formula (CI). R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ isindependently a hydrogen, C₁-C₄₀ hydrocarbyl, C₁-C₄₀ substitutedhydrocarbyl, a functional group comprising elements from Groups 13 to17, or two or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²,R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,R²⁷, and R²⁸ may independently join together to form a C₄-C₆₂ cyclic orpolycyclic ring structure, or a combination thereof; R¹¹ and R¹² mayjoin together to form a five- to eight-membered heterocycle; Q* is agroup 15 or 16 atom; z is 0 or 1; J* is CR″ or N, and G* is CR″ or N,where R″ is C₁-C₂₀ hydrocarbyl or carbonyl-containing C₁-C₂₀hydrocarbyl; and z=0 if Q* is a group 16 atom, and z=1 if Q* is a group15 atom.

In at least one embodiment the catalyst is an iron complex representedby formula (IV):

wherein:

A is chlorine, bromine, iodine, —CF₃ or —OR¹¹;

each of R¹ and R² is independently hydrogen, C₁-C₂₂-alkyl,C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl where alkyl has from 1 to 10carbon atoms and aryl has from 6 to 20 carbon atoms, or five-, six- orseven-membered heterocycle comprising at least one atom selected fromthe group consisting of N, P, O and S;

wherein each of R¹ and R² is optionally substituted by halogen, —NR¹¹ ₂,—OR¹¹ or —SiR¹² ₃;

wherein R¹ optionally bonds with R³, and R² optionally bonds with R⁵, ineach case to independently form a five-, six- or seven-membered ring; R⁷is a C₁-C₂₀ alkyl;

each of R³, R⁴, R⁵, R⁸, R⁹, R¹⁰, R¹⁵, R¹⁶, and R¹⁷ is independentlyhydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl wherealkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbonatoms, —NR¹¹ ₂, —OR¹¹, halogen, —SiR¹² ₃ or five-, six- orseven-membered heterocycle comprising at least one atom selected fromthe group consisting of N, P, O, and S;

wherein R³, R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹⁵, R¹⁶, and R¹⁷ are optionallysubstituted by halogen, —NR¹¹ ₂, —OR¹¹ or —SiR¹² ₃;

wherein R³ optionally bonds with R⁴, R⁴ optionally bonds with R⁵, R⁷optionally bonds with R¹⁰, R¹⁰ optionally bonds with R⁹, R⁹ optionallybonds with R⁸, R¹⁷ optionally bonds with R¹⁶, and R¹⁶ optionally bondswith R¹⁵, in each case to independently form a five-, six- orseven-membered carbocyclic or heterocyclic ring, the heterocyclic ringcomprising at least one atom from the group consisting of N, P, O and S;

R¹³ is C₁-C₂₀-alkyl bonded with the aryl ring via a primary or secondarycarbon atom;

R¹⁴ is chlorine, bromine, iodine, —CF₃ or —OR¹¹, or C₁-C₂₀-alkyl bondedwith the aryl ring;

each R¹¹ is independently hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl,C₆-C₂₂-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms andaryl has from 6 to 20 carbon atoms, or —SiR¹² ₃, wherein R¹¹ isoptionally substituted by halogen, or two R¹¹ radicals optionally bondto form a five- or six-membered ring;

-   -   each R¹² is independently hydrogen, C₁-C₂₂-alkyl,        C₂-C₂₂-alkenyl, C₆-C₂₂-aryl, arylalkyl where alkyl has from 1 to        10 carbon atoms and aryl has from 6 to 20 carbon atoms, or two        R¹² radicals optionally bond to form a five- or six-membered        ring;

each of E¹, E², and E³ is independently carbon, nitrogen or phosphorus;

each u is independently 0 if E¹, E², and E³ is nitrogen or phosphorusand is 1 if E¹, E², and E³ is carbon;

each X is independently fluorine, chlorine, bromine, iodine, hydrogen,C₁-C₂₀-alkyl, C₂-C₁₀-alkenyl, C₆-C₂₀-aryl, arylalkyl where alkyl hasfrom 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —NR¹⁸₂, —OR¹⁸, —SR¹⁸, —SO₃R¹⁸, —OC(O)R¹⁸, —CN, —SCN, β-diketonate, —CO, —BF₄⁻, —PF₆ ⁻ or bulky non-coordinating anions, and the radicals X can bebonded with one another;

each R¹⁸ is independently hydrogen, C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,C₆-C₂₀-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms andaryl has from 6 to 20 carbon atoms, or —SiR¹⁹ ₃, wherein R¹⁸ can besubstituted by halogen or nitrogen- or oxygen-containing groups and twoR¹⁸ radicals optionally bond to form a five- or six-membered ring;

each R¹⁹ is independently hydrogen, C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,C₆-C₂₀-aryl or arylalkyl where alkyl has from 1 to 10 carbon atoms andaryl has from 6 to 20 carbon atoms, wherein R¹⁹ can be substituted byhalogen or nitrogen- or oxygen-containing groups or two R¹⁹ radicalsoptionally bond to form a five- or six-membered ring;

s is 1, 2, or 3;

D is a neutral donor; and

t is 0 to 2.

In another embodiment, the catalyst is a phenoxyimine compoundrepresented by the formula (VII):

wherein M represents a transition metal atom selected from the groups 3to 11 metals in the periodic table; k is an integer of 1 to 6; m is aninteger of 1 to 6; R^(a) to R^(f) may be the same or different from oneanother and each represent a hydrogen atom, a halogen atom, ahydrocarbon group, a heterocyclic compound residue, an oxygen-containinggroup, a nitrogen-containing group, a boron-containing group, asulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group or atin-containing group, among which 2 or more groups may be bound to eachother to form a ring; when k is 2 or more, R^(a) groups, R^(b) groups,R^(c) groups, R^(d) groups, R^(e) groups, or R^(f) groups may be thesame or different from one another, one group of R^(a) to R^(f)contained in one ligand and one group of R^(a) to R^(f) contained inanother ligand may form a linking group or a single bond, and aheteroatom contained in R^(a) to R^(f) may coordinate with or bind to M;m is a number satisfying the valence of M; Q represents a hydrogen atom,a halogen atom, an oxygen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group; when m is 2 or more, a plurality of groupsrepresented by Q may be the same or different from one another, and aplurality of groups represented by Q may be mutually bound to form aring.

In another embodiment, the catalyst is a bis(imino)pyridyl of theformula (VIII):

wherein:

M is Co or Fe; each X is an anion; n is 1, 2 or 3, so that the totalnumber of negative charges on said anion or anions is equal to theoxidation state of a Fe or Co atom present in (VIII);

R¹, R² and R³ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl, or an inert functional group;

R⁴ and R⁵ are each independently hydrogen, hydrocarbyl, an inertfunctional group or substituted hydrocarbyl;

R⁶ is formula (IX):

and R⁷ is formula (X):

R⁸ and R¹³ are each independently hydrocarbyl, substituted hydrocarbylor an inert functional group;

R⁹, R¹⁰, R¹¹, R¹⁴, R¹⁵ and R¹⁶ are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or an inert functional group;

R¹² and R¹⁷ are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or an inert functional group;

and provided that any two of R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶and R¹⁷ that are adjacent to one another, together may form a ring.

In at least one embodiment, the catalyst compound is represented by theformula (XI):

M¹ is selected from the group consisting of titanium, zirconium,hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten.In at least one embodiment, M¹ is zirconium.

Each of Q¹, Q², Q³, and Q⁴ is independently oxygen or sulfur. In atleast one embodiment, at least one of Q¹, Q², Q³, and Q⁴ is oxygen,alternately all of Q¹, Q², Q³, and Q⁴ are oxygen.

R¹ and R² are independently hydrogen, halogen, hydroxyl, hydrocarbyl, orsubstituted hydrocarbyl (such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₆-C₂₀aryl, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄₀ arylalkyl,C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, or conjugated diene which isoptionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl or tri(hydrocarbyl) silylhydrocarbyl, the diene having up to 30atoms other than hydrogen). R¹ and R² can be a halogen selected fromfluorine, chlorine, bromine, or iodine. Preferably, R¹ and R² arechlorine.

Alternatively, R¹ and R² may also be joined together to form analkanediyl group or a conjugated C₄-C₄₀ diene ligand which iscoordinated to M¹. R¹ and R² may also be identical or differentconjugated dienes, optionally substituted with one or more hydrocarbyl,tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, the dieneshaving up to 30 atoms not counting hydrogen and/or forming a π-complexwith M¹.

Exemplary groups suitable for R¹ and or R² can include 1,4-diphenyl,1,3-butadiene, 1,3-pentadiene, 2-methyl 1,3-pentadiene, 2,4-hexadiene,1-phenyl, 1,3-pentadiene, 1,4-dibenzyl, 1,3-butadiene,1,4-ditolyl-1,3-butadiene, 1,4-bis (trimethylsilyl)-1,3-butadiene, and1,4-dinaphthyl-1,3-butadiene. R¹ and R² can be identical and are C₁-C₃alkyl or alkoxy, C₆-C₁₀ aryl or aryloxy, C₂-C₄ alkenyl, C₇-C₁₀arylalkyl, C₇-C₁₂ alkylaryl, or halogen.

Each of R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, and R¹⁹ is independently hydrogen, halogen, C₁-C₄₀ hydrocarbyl orC₁-C₄₀ substituted hydrocarbyl (such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy,C₆-C₂₀ aryl, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄₀arylalkyl, C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, or conjugated dienewhich is optionally substituted with one or more hydrocarbyl,tri(hydrocarbyl) silyl or tri(hydrocarbyl) silylhydrocarbyl, the dienehaving up to 30 atoms other than hydrogen), —NR′₂, —SR′, —OR, —OSiR′₃,—PR′₂, where each R′ is hydrogen, halogen, C₁-C₁₀ alkyl, or C₆-C₁₀ aryl,or one or more of R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R⁸ and R⁹, R⁹ andR¹⁰, R¹⁰ and R¹¹, R¹² and R¹³, R¹³ and R¹⁴, R¹⁴ and R¹⁵, R¹⁶ and R¹⁷,R¹⁷ and R¹⁸, and R¹⁸ and R¹⁹ are joined to form a saturated ring,unsaturated ring, substituted saturated ring, or substituted unsaturatedring. In at least one embodiment, C₁-C₄₀ hydrocarbyl is selected frommethyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl,sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl,sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, andsec-decyl. Preferably, R¹¹ and R¹² are C₆-C₁₀ aryl such as phenyl ornaphthyl optionally substituted with C₁-C₄₀ hydrocarbyl, such as C₁-C₁₀hydrocarbyl. Preferably, R⁶ and R¹⁷ are C₁₋₄₀ alkyl, such as C₁-C₁₀alkyl.

In at least one embodiment, each of R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ is independently hydrogen or C₁-C₄₀hydrocarbyl. In at least one embodiment, C₁-C₄₀ hydrocarbyl is selectedfrom methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl,sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl,sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, andsec-decyl. Preferably, each of R⁶ and R¹⁷ is C₁-C₄₀ hydrocarbyl and R⁴,R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁸, and R¹⁹ is hydrogen. In atleast one embodiment, C₁-C₄₀ hydrocarbyl is selected from methyl, ethyl,propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl,isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl,isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl,sec-nonyl, n-decyl, isodecyl, and sec-decyl.

R³ is a C₁-C₄₀ unsaturated alkyl or substituted C₁-C₄₀ unsaturated alkyl(such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₆-C₂₀ aryl, C₆-C₁₀ aryloxy,C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄₀ arylalkyl, C₇-C₄₀ alkylaryl,C₈-C₄₀ arylalkenyl, or conjugated diene which is optionally substitutedwith one or more hydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl)silylhydrocarbyl, the diene having up to 30 atoms other than hydrogen).

Preferably, R³ is a hydrocarbyl comprising a vinyl moiety. As usedherein, “vinyl” and “vinyl moiety” are used interchangeably and includea terminal alkene, e.g., represented by the structure

Hydrocarbyl of R³ may be further substituted (such as C₁-C₁₀ alkyl,C₁-C₁₀ alkoxy, C₆-C₂₀ aryl, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl, C₂-C₄₀alkenyl, C₇-C₄₀ arylalkyl, C₇-C₄₀ alkylaryl, C₈-C₄₀ arylalkenyl, orconjugated diene which is optionally substituted with one or morehydrocarbyl, tri(hydrocarbyl) silyl or tri(hydrocarbyl)silylhydrocarbyl, the diene having up to 30 atoms other than hydrogen).Preferably, R³ is C₁-C₄₀ unsaturated alkyl that is vinyl or substitutedC₁-C₄₀ unsaturated alkyl that is vinyl. R³ can be represented by thestructure —R′CH═CH₂ where R′ is C₁-C₄₀ hydrocarbyl or C₁-C₄₀ substitutedhydrocarbyl (such as C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₆-C₂₀ aryl, C₆-C₁₀aryloxy, C₂-C₁₀ alkenyl, C₂-C₄₀ alkenyl, C₇-C₄₀ arylalkyl, C₇-C₄₀alkylaryl, C₈-C₄₀ arylalkenyl, or conjugated diene which is optionallysubstituted with one or more hydrocarbyl, tri(hydrocarbyl) silyl ortri(hydrocarbyl) silylhydrocarbyl, the diene having up to 30 atoms otherthan hydrogen). In at least one embodiment, C₁-C₄₀ hydrocarbyl isselected from methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl,sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl,sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, andsec-decyl.

In at least one embodiment, R³ is 1-propenyl, 1-butenyl, 1-pentenyl,1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, or 1-decenyl.

In at least one embodiment, the catalyst is a Group 15-containing metalcompound represented by formulas (XII) or (XIII):

wherein M is a Group 3 to 12 transition metal or a Group 13 or 14 maingroup metal, a Group 4, 5, or 6 metal. In many embodiments, M is a Group4 metal, such as zirconium, titanium, or hafnium. Each X isindependently a leaving group, such as an anionic leaving group. Theleaving group may include a hydrogen, a hydrocarbyl group, a heteroatom,a halogen, or an alkyl; y is 0 or 1 (when y is 0 group L′ is absent).The term ‘n’ is the oxidation state of M. In various embodiments, n is+3, +4, or +5. In many embodiments, n is +4. The term ‘m’ represents theformal charge of the YZL or the YZL′ ligand, and is 0, −1, −2 or −3 invarious embodiments. In many embodiments, m is −2. L is a Group 15 or 16element, such as nitrogen or oxygen; L′ is a Group 15 or 16 element orGroup 14 containing group, such as carbon, silicon or germanium. Y is aGroup 15 element, such as nitrogen or phosphorus. In many embodiments, Yis nitrogen. Z is a Group 15 element, such as nitrogen or phosphorus. Inmany embodiments, Z is nitrogen. R¹ and R² are, independently, a C₁ toC₂₀ hydrocarbon group, a heteroatom containing group having up to twentycarbon atoms, silicon, germanium, tin, lead, or phosphorus. In manyembodiments, R¹ and R² are a C₂ to C₂₀ alkyl, aryl or aralkyl group,such as a C₂ to C₂₀ linear, branched or cyclic alkyl group, or a C₂ toC₂₀ hydrocarbon group. R¹ and R² may also be interconnected to eachother. R³ may be absent or may be a hydrocarbon group, a hydrogen, ahalogen, a heteroatom containing group. In many embodiments, R³ isabsent, for example, if L is an oxygen, or a hydrogen, or a linear,cyclic, or branched alkyl group having 1 to 20 carbon atoms. R⁴ and R⁵are independently an alkyl group, an aryl group, substituted aryl group,a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkylgroup, a substituted cyclic aralkyl group, or multiple ring system,often having up to 20 carbon atoms. In many embodiments, R⁴ and R⁵ havebetween 3 and 10 carbon atoms, or are a C₁ to C₂₀ hydrocarbon group, aC₁ to C₂₀ aryl group or a C₁ to C₂₀ aralkyl group, or a heteroatomcontaining group. R⁴ and R⁵ may be interconnected to each other. R⁶ andR⁷ are independently absent, hydrogen, an alkyl group, halogen,heteroatom, or a hydrocarbyl group, such as a linear, cyclic or branchedalkyl group having 1 to 20 carbon atoms. In many embodiments, R⁶ and R⁷are absent. R* may be absent, or may be a hydrogen, a Group 14 atomcontaining group, a halogen, or a heteroatom containing group.

By “formal charge of the YZL or YZL′ ligand,” it is meant the charge ofthe entire ligand absent the metal and the leaving groups X. By “R¹ andR² may also be interconnected” it is meant that R¹ and R² may bedirectly bound to each other or may be bound to each other through othergroups. By “R⁴ and R⁵ may also be interconnected” it is meant that R⁴and R⁵ may be directly bound to each other or may be bound to each otherthrough other groups. An alkyl group may be linear, branched alkylradicals, alkenyl radicals, alkynyl radicals, cycloalkyl radicals, arylradicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxyradicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonylradicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An aralkyl group is defined to be a substitutedaryl group.

In one or more embodiments, R⁴ and R⁵ are independently a grouprepresented by structure (XIV):

wherein R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkylgroup, a halide, a heteroatom, a heteroatom containing group containingup to 40 carbon atoms. In many embodiments, R⁸ to R¹² are a C₁ to C₂₀linear or branched alkyl group, such as a methyl, ethyl, propyl, orbutyl group. Any two of the R groups may form a cyclic group and/or aheterocyclic group. The cyclic groups may be aromatic. In one embodimentR⁹, R¹⁰ and R¹² are independently a methyl, ethyl, propyl, or butylgroup (including all isomers). In another embodiment, R⁹, R¹⁰ and R¹²are methyl groups, and R⁸ and R¹¹ are hydrogen.

In one or more embodiments, R⁴ and R⁵ are both a group represented bystructure (XV):

wherein M is a Group 4 metal, such as zirconium, titanium, or hafnium.In at least one embodiment, M is zirconium. Each of L, Y, and Z may be anitrogen. Each of R¹ and R² may be —CH₂—CH₂—. R³ may be hydrogen, and R⁶and R⁷ may be absent.

In preferred embodiments, the catalyst compounds described inPCT/US2018/051345, filed Sep. 17, 2018 may be used with the activatorsdescribed herein, particularly the catalyst compounds described at Page16 to Page 32 of the application as filed.

In some embodiments, a co-activator is combined with the catalystcompound (such as halogenated catalyst compounds described above) toform an alkylated catalyst compound. Organoaluminum compounds which maybe utilized as co-activators include, for example, trialkyl aluminumcompounds, such as trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and thelike, or alumoxanes.

In some embodiments, two or more different catalyst compounds arepresent in the catalyst system used herein. In some embodiments, two ormore different catalyst compounds are present in the reaction zone wherethe process(es) described herein occur. When two transition metalcompound-based catalysts are used in one reactor as a mixed catalystsystem, the two transition metal compounds are preferably chosen suchthat the two are compatible. A simple screening method such as by ¹H or¹³C NMR, known to those of ordinary skill in the art, can be used todetermine which transition metal compounds are compatible. It ispreferable to use the same activator for the transition metal compounds;however, two different activators can be used in combination. If one ormore transition metal compounds contain an anionic ligand as a leavinggroup which is not a hydride, hydrocarbyl, or substituted hydrocarbyl,then the alumoxane or other alkyl aluminum is typically contacted withthe transition metal compounds prior to addition of the non-coordinatinganion activator.

The two transition metal compounds (pre-catalysts) may be used in anyratio. Preferred molar ratios of (A) transition metal compound to (B)transition metal compound fall within the range of (A:B) 1:1000 to1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1,alternatively 1:1 to 100:1, and alternatively 1:1 to 75:1, andalternatively 5:1 to 50:1. The particular ratio chosen will depend onthe exact pre-catalysts chosen, the method of activation, and the endproduct desired. In a particular embodiment, when using the twopre-catalysts, where both are activated with the same activator, usefulmole percents, based upon the molecular weight of the pre-catalysts, are10 to 99.9% A to 0.1 to 90% B, alternatively 25 to 99% A to 0.5 to 50%B, alternatively 50 to 99% A to 1 to 25% B, and alternatively 75 to 99%A to 1 to 10% B.

Support Materials

In embodiments herein, the catalyst system may comprise a supportmaterial. In at least one embodiment, the support material is a poroussupport material, for example, talc, or inorganic oxides. Other supportmaterials include zeolites, clays, organoclays, or any other suitableorganic or inorganic support material and the like, or mixtures thereof.

In at least one embodiment, the support material is an inorganic oxide.Suitable inorganic oxide materials for use in catalyst systems hereininclude Groups 2, 4, 13, and 14 metal oxides, such as silica, alumina,and mixtures thereof. Other inorganic oxides that may be employed eitheralone or in combination with the silica, or alumina are magnesia,titania, zirconia, and the like. Other suitable support materials,however, can be used, for example, functionalized polyolefins, such aspolypropylene. Supports include magnesia, titania, zirconia,montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.Also, combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania, and the like. Supportmaterials include Al₂O₃, ZrO₂, SiO₂, SiO₂/Al₂O₃, SiO₂/TiO₂, silica clay,silicon oxide/clay, or mixtures thereof.

The support material, such as an inorganic oxide, can have a surfacearea of from 10 m²/g to 700 m²/g, pore volume in the range of from 0.1cc/g to 4.0 cc/g and average particle size in the range of from 5 μm to500 μm. In at least one embodiment, the surface area of the supportmaterial is in the range of from 50 m²/g to 500 m²/g, pore volume offrom 0.5 cc/g to 3.5 cc/g and average particle size of from 10 μm to 200μm. In at least one embodiment, the surface area of the support materialis in the range is from 100 m²/g to 400 m²/g, pore volume from 0.8 cc/gto 3.0 cc/g and average particle size is from 5 μm to 100 μm. Theaverage pore size of the support material useful in the presentdisclosure is in the range of from 10 Å to 1000 Å, such as 50 Å to 500Å, such as 75 Å to 350 Å. In some embodiments, the support material is ahigh surface area, amorphous silica (surface area=300 m²/gm; pore volumeof 1.65 cm³/gm). Exemplary silicas are marketed under the tradenames ofDAVISON 952 or DAVISON 955 by the Davison Chemical Division of W.R.Grace and Company. In other embodiments DAVISON 948 is used.

The support material should be dry, that is, substantially free ofabsorbed water. Drying of the support material can be effected byheating or calcining at 100° C. to 1,000° C., such as at least about600° C. When the support material is silica, it is heated to at least200° C., such as 200° C. to 850° C., such as at about 600° C.; and for atime of 1 minute to about 100 hours, from 12 hours to 72 hours, or from24 hours to 60 hours. The calcined support material should have at leastsome reactive hydroxyl (OH) groups to produce supported catalyst systemsof the present disclosure. The calcined support material is thencontacted with at least one polymerization catalyst comprising at leastone catalyst compound and an activator.

The support material, having reactive surface groups, typically hydroxylgroups, is slurried in a non-polar solvent and the resulting slurry iscontacted with a solution of a catalyst compound and an activator. Insome embodiments, the slurry of the support material is first contactedwith the activator for a period of time in the range of from 0.5 hoursto 24 hours, from 2 hours to 16 hours, or from 4 hours to 8 hours. Thesolution of the catalyst compound is then contacted with the isolatedsupport/activator. In some embodiments, the supported catalyst system isgenerated in situ. In at least one embodiment, the slurry of the supportmaterial is first contacted with the catalyst compound for a period oftime in the range of from 0.5 hours to 24 hours, from 2 hours to 16hours, or from 4 hours to 8 hours. The slurry of the supported catalystcompound is then contacted with the activator solution.

The mixture of the catalyst, activator and support is heated to 0° C. to70° C., such as to 23° C. to 60° C., such as at room temperature.Contact times typically range from 0.5 hours to 24 hours, from 2 hoursto 16 hours, or from 4 hours to 8 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, e.g., the activator, and the catalyst compound, are atleast partially soluble and which are liquid at room temperature.Non-limiting example non-polar solvents are alkanes, such as isopentane,hexane, n-heptane, octane, nonane, and decane, cycloalkanes, such ascyclohexane, aromatics, such as benzene, toluene, and ethylbenzene.

In at least one embodiment, the support material comprises a supportmaterial treated with an electron-withdrawing anion. The supportmaterial can be silica, alumina, silica-alumina, silica-zirconia,alumina-zirconia, aluminum phosphate, heteropolytungstates, titania,magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof;and the electron-withdrawing anion is selected from fluoride, chloride,bromide, phosphate, triflate, bisulfate, sulfate, or any combinationthereof.

The electron-withdrawing component used to treat the support materialcan be any component that increases the Lewis or Brønsted acidity of thesupport material upon treatment (as compared to the support materialthat is not treated with at least one electron-withdrawing anion). In atleast one embodiment, the electron-withdrawing component is anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Electron-withdrawing anions can be sulfate,bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate,fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate,fluorozirconate, fluorotitanate, phospho-tungstate, or mixtures thereof,or combinations thereof. An electron-withdrawing anion can be fluoride,chloride, bromide, phosphate, triflate, bisulfate, or sulfate, or anycombination thereof, at least one embodiment of this disclosure. In atleast one embodiment, the electron-withdrawing anion is sulfate,bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate,fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate,fluorozirconate, fluorotitanate, or combinations thereof.

Thus, for example, the support material suitable for use in the catalystsystems of the present disclosure can be one or more of fluoridedalumina, chlorided alumina, bromided alumina, sulfated alumina,fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, or combinations thereof. In at least one embodiment, theactivator-support can be, or can comprise, fluorided alumina, sulfatedalumina, fluorided silica-alumina, sulfated silica-alumina, fluoridedsilica-coated alumina, sulfated silica-coated alumina, phosphatedsilica-coated alumina, or combinations thereof. In another embodiment,the support material includes alumina treated with hexafluorotitanicacid, silica-coated alumina treated with hexafluorotitanic acid,silica-alumina treated with hexafluorozirconic acid, silica-aluminatreated with trifluoroacetic acid, fluorided boria-alumina, silicatreated with tetrafluoroboric acid, alumina treated withtetrafluoroboric acid, alumina treated with hexafluorophosphoric acid,or combinations thereof. Further, any of these activator-supportsoptionally can be treated with a metal ion.

Nonlimiting examples of cations suitable for use in the presentdisclosure in the salt of the electron-withdrawing anion includeanilinium, trialkyl anilinium, tetraalkyl anilinium, or combinationsthereof.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the support material to a desired level. Combinations ofelectron-withdrawing components can be contacted with the supportmaterial simultaneously or individually, and in any order that providesa desired chemically-treated support material acidity. For example, inat least one embodiment, two or more electron-withdrawing anion sourcecompounds in two or more separate contacting steps.

In at least one embodiment of the present disclosure, one example of aprocess by which a chemically-treated support material is prepared is asfollows: a selected support material, or combination of supportmaterials, can be contacted with a first electron-withdrawing anionsource compound to form a first mixture; such first mixture can becalcined and then contacted with a second electron-withdrawing anionsource compound to form a second mixture; the second mixture can then becalcined to form a treated support material. In such a process, thefirst and second electron-withdrawing anion source compounds can beeither the same or different compounds.

The method by which the oxide is contacted with the electron-withdrawingcomponent, typically a salt or an acid of an electron-withdrawing anion,can include gelling, co-gelling, impregnation of one compound ontoanother, or combinations thereof. Following a contacting method, thecontacted mixture of the support material, electron-withdrawing anion,and optional metal ion, can be calcined.

According to another embodiment of the present disclosure, the supportmaterial can be treated by a process comprising: (i) contacting asupport material with a first electron-withdrawing anion source compoundto form a first mixture; (ii) calcining the first mixture to produce acalcined first mixture; (iii) contacting the calcined first mixture witha second electron-withdrawing anion source compound to form a secondmixture; and (iv) calcining the second mixture to form the treatedsupport material.

Polymer Processes

In embodiments herein, the present disclosure provides polymerizationprocesses where monomer (such as propylene or ethylene), and optionallycomonomer, are contacted with a catalyst system comprising an activatorand at least one catalyst compound, as described above. The catalystcompound and activator may be combined in any order, and are combinedtypically prior to contacting with the monomer.

In at least one embodiment, a polymerization process includes a)contacting one or more olefin monomers with a catalyst systemcomprising: i) an activator and ii) a catalyst compound of the presentdisclosure. The activator is a non-coordination anion activator. The oneor more olefin monomers may be propylene and/or ethylene and thepolymerization process further comprises heating the one or more olefinmonomers and the catalyst system to 70° C. or more to form propylenepolymers or ethylene polymers, such as propylene polymers.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, such as C₂ to C₂₀ alpha olefins, such as C₂ to C₁₂ alphaolefins, such as ethylene, propylene, butene, pentene, hexene, heptene,octene, nonene, decene, undecene, dodecene and isomers thereof. In atleast one embodiment, the monomer comprises propylene and an optionalcomonomers comprising one or more propylene or C₄ to C₄₀ olefins, suchas C₄ to C₂₀ olefins, such as C₆ to C₁₂ olefins. The C₄ to C₄₀ olefinmonomers may be linear, branched, or cyclic. The C₄ to C₄₀ cyclicolefins may be strained or unstrained, monocyclic or polycyclic, and mayoptionally include heteroatoms and/or one or more functional groups. Inat least one embodiment, the monomer comprises propylene and an optionalcomonomers comprising one or more C₃ to C₄₀ olefins, such as C₄ to C₂₀olefins, such as C₆ to C₁₂ olefins. The C₃ to C₄₀ olefin monomers may belinear, branched, or cyclic. The C₃ to C₄₀ cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and/or one or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers includepropylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof, such as hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene,norbornadiene, and their respective homologs and derivatives, such asnorbornene, norbornadiene, and dicyclopentadiene.

In at least one embodiment, one or more dienes are present in thepolymer produced herein at up to 10 wt %, such as at 0.00001 to 1.0 wt%, such as 0.002 to 0.5 wt %, such as 0.003 to 0.2 wt %, based upon thetotal weight of the composition. In some embodiments, 500 ppm or less ofdiene is added to the polymerization, such as 400 ppm or less, such as300 ppm or less. In other embodiments at least 50 ppm of diene is addedto the polymerization, or 100 ppm or more, or 150 ppm or more.

Diene monomers include any hydrocarbon structure, such as C₄ to C₃₀,having at least two unsaturated bonds, wherein at least two of theunsaturated bonds are readily incorporated into a polymer by either astereospecific or a non-stereospecific catalyst(s). The diene monomerscan be selected from alpha, omega-diene monomers (i.e. di-vinylmonomers). The diolefin monomers are linear di-vinyl monomers, such asthose containing from 4 to 30 carbon atoms. Examples of dienes includebutadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene,decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene,pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene,nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene,tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene,octacosadiene, nonacosadiene, triacontadiene, 1,6-heptadiene,1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene,1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and lowmolecular weight polybutadienes (Mw less than 1000 g/mol). Cyclic dienesinclude cyclopentadiene, vinylnorbornene, norbornadiene, ethylidenenorbornene, divinylbenzene, dicyclopentadiene or higher ring containingdiolefins with or without substituents at various ring positions.

Polymerization processes of the present disclosure can be carried out inany suitable manner. Any suitable suspension, homogeneous, bulk,solution, slurry, or gas phase polymerization process can be used. Suchprocesses can be run in a batch, semi-batch, or continuous mode.Homogeneous polymerization processes and slurry processes can beperformed. (A useful homogeneous polymerization process is one where atleast 90 wt % of the product is soluble in the reaction media.) A bulkhomogeneous process can be used. (An example bulk process is one wheremonomer concentration in all feeds to the reactor is 70 volume % ormore.) Alternately, no solvent or diluent is present or added in thereaction medium, (except for the small amounts used as the carrier forthe catalyst system or other additives, or amounts typically found withthe monomer; e.g., propane in propylene). In at least one embodiment,the process is a slurry polymerization process. As used herein the term“slurry polymerization process” means a polymerization process where asupported catalyst is employed and monomers are polymerized on thesupported catalyst particles. At least 95 wt % of polymer productsderived from the supported catalyst are in granular form as solidparticles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄-C₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefinswhich may act as monomers or comonomers including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, 1-decene, and mixtures thereof. In at least one embodiment,the solvent is not aromatic, such that aromatics are present in thesolvent at less than 1 wt %, such as less than 0.5 wt %, such as lessthan 0 wt % based upon the weight of the solvents.

In at least one embodiment, the feed concentration of the monomers andcomonomers for the polymerization is 60 vol % solvent or less, such as40 vol % or less, such as 20 vol % or less, based on the total volume ofthe feedstream. The polymerization can be performed in a bulk process.

Polymerizations can be performed at any temperature and/or pressuresuitable to obtain the desired polymers, such as ethylene and orpropylene polymers. Typical temperatures and/or pressures include atemperature in the range of from 0° C. to 300° C., such as 20° C. to200° C., such as 35° C. to 150° C., such as 40° C. to 120° C., such as45° C. to 80° C., for example about 74° C., and at a pressure in therange of from 0.35 MPa to 10 MPa, such as 0.45 MPa to 6 MPa, such as 0.5MPa to 4 MPa.

In a typical polymerization, the run time of the reaction is up to 300minutes, such as in the range of from 5 to 250 minutes, such as 10 to120 minutes.

In at least one embodiment, hydrogen is present in the polymerizationreactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa),such as from 0.01 to 25 psig (0.07 to 172 kPa), such as 0.1 to 10 psig(0.7 to 70 kPa).

In at least one embodiment, the activity of the catalyst is from 50gP/mmolCat/hour to 200,000 gP/mmolCat/hr, such as from 10,000gP/mmolCat/hr to 150,000 gP/mmolCat/hr, such as from 40,000gP/mmolCat/hr to 100,000 gP/mmolCat/hr, such as about 50,000gP/mmolCat/hr or more, such as 70,000 gP/mmolCat/hr or more. In at leastone embodiment, the conversion of olefin monomer is at least 10%, basedupon polymer yield and the weight of the monomer entering the reactionzone, such as 20% or more, such as 30% or more, such as 50% or more,such as 80% or more.

In at least one embodiment, a catalyst system of the present disclosureis capable of producing a polyolefin. In at least one embodiment, apolyolefin is a homopolymer of ethylene or propylene or a copolymer ofethylene such as a copolymer of ethylene having from 0.1 to 25 wt %(such as from 0.5 to 20 wt %, such as from 1 to 15 wt %, such as from 5to 17 wt %) of ethylene with the remainder balance being one or more C₃to C₂₀ olefin comonomers (such as C₃ to C₁₂ alpha-olefin, such aspropylene, butene, hexene, octene, decene, dodecene, such as propylene,butene, hexene, octene). A polyolefin can be a copolymer of propylenesuch as a copolymer of propylene having from 0.1 to 25 wt % (such asfrom 0.5 to 20 wt %, such as from 1 to 15 wt %, such as from 3 to 10 wt%) of propylene and from 99.9 to 75 wt % of one or more of C₂ or C₄ toC₂₀ olefin comonomer (such as ethylene or C₄ to C₁₂ alpha-olefin, suchas butene, hexene, octene, decene, dodecene, such as ethylene, butene,hexene, octene).

In at least one embodiment, a catalyst system of the present disclosureis capable of producing polyolefins, such as polypropylene (e.g., iPP)or ethylene-octene copolymers, having an Mw from 40,000 to 1,500,000,such as from 70,000 to 1,000,000, such as from 90,000 to 500,000, suchas from 90,000 to 250,000, such as from 90,000 to 200,000, such as from90,000 to 110,000.

In at least one embodiment, a catalyst system of the present disclosureis capable of producing polyolefins, such as polypropylene (e.g., iPP)or ethylene-octene copolymers, having an Mn from 5,000 to 1,000,000,such as from 20,000 to 160,000, such as from 30,000 to 70,000, such asfrom 40,000 to 70,000. In at least one embodiment, a catalyst system ofthe present disclosure is capable of producing propylene polymers havingan Mw/Mn value from 1 to 10, such as from 1.5 to 9, such as from 2 to 7,such as from 2 to 4, such as from 2.5 to 3, for example about 2.

In at least one embodiment, a catalyst system of the present disclosureis capable of producing polyolefins, such as polypropylene (e.g., iPP)or ethylene-octene copolymers, having a melt temperature (Tm) of from100° C. to 150° C., such as 110° C. to 140° C., such as 120° C. to 135°C., such as 130° C. to 135° C.

In at least one embodiment, little or no scavenger is used in theprocess to produce polymer, such as propylene polymer. Scavenger (suchas trialkyl aluminum) can be present at zero mol %, alternately thescavenger is present at a molar ratio of scavenger metal to transitionmetal of less than 100:1, such as less than 50:1, such as less than15:1, such as less than 10:1.

In at least one embodiment, the polymerization: 1) is conducted attemperatures of 0 to 300° C. (such as 25 to 150° C., such as 40 to 120°C., such as 70 to 110° C., such as 85 to 100° C.); 2) is conducted at apressure of atmospheric pressure to 10 MPa (such as 0.35 to 10 MPa, suchas from 0.45 to 6 MPa, such as from 0.5 to 4 MPa); 3) is conducted in analiphatic hydrocarbon solvent (such as isobutane, butane, pentane,isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixturesthereof; cyclic and alicyclic hydrocarbons, such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof, where aromatics are present in the solvent at less than 1 wt %,such as less than 0.5 wt %, such as at 0 wt % based upon the weight ofthe solvents); and 4) the productivity of the catalyst compound is atleast 30,000 gP/mmolCat/hr (such as at least 50,000 gP/mmolCat/hr, suchas at least 60,000 gP/mmolCat/hr, such as at least 80,000 gP/mmolCat/hr,such as at least 100,000 gP/mmolCat/hr).

In at least one embodiment, the catalyst system used in thepolymerization comprises no more than one catalyst compound. A “reactionzone” also referred to as a “polymerization zone” is a vessel wherepolymerization takes place, for example a batch reactor. When multiplereactors are used in either series or parallel configuration, eachreactor is considered as a separate polymerization zone. For amulti-stage polymerization in both a batch reactor and a continuousreactor, each polymerization stage is considered as a separatepolymerization zone. In at least one embodiment, the polymerizationoccurs in one reaction zone.

Other additives may also be used in the polymerization, as desired, suchas one or more scavengers, promoters, modifiers, chain transfer agents(such as diethyl zinc), hydrogen, or aluminum alkyls. Useful chaintransfer agents are typically alkylalumoxanes, a compound represented bythe formula AlR₃, ZnR₂ (where each R is, independently, a C₁-C₈aliphatic radical, such as methyl, ethyl, propyl, butyl, phenyl, hexyl,octyl or an isomer thereof) or a combination thereof, such as diethylzinc, methylalumoxane, trimethylaluminum, triisobutylaluminum,trioctylaluminum, or a combination thereof.

Gas Phase Polymerization

Generally, in a fluidized gas bed process used for producing polymers, agaseous stream containing one or more monomers is continuously cycledthrough a fluidized bed in the presence of a catalyst under reactiveconditions. The gaseous stream is withdrawn from the fluidized bed andrecycled back into the reactor. Simultaneously, polymer product iswithdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. (See, for example, U.S. Pat. Nos. 4,543,399;4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304;5,453,471; 5,462,999; 5,616,661; and 5,668,228; all of which are fullyincorporated herein by reference.)

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068 kPa) oreven greater and temperatures in the range of 0° C. to about 120° C. Ina slurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization diluent medium to which monomer andcomonomers, along with catalysts, are added. The suspension includingdiluent is intermittently or continuously removed from the reactor wherethe volatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluent usedin the polymerization medium is typically an alkane having from 3 to 7carbon atoms, such as a branched alkane. The medium employed should beliquid under the conditions of polymerization and relatively inert. Whena propane medium is used, the process must be operated above thereaction diluent critical temperature and pressure. For example, ahexane or an isobutane medium is employed.

In at least one embodiment, a polymerization process is a particle formpolymerization, or a slurry process, where the temperature is kept belowthe temperature at which the polymer goes into solution. Such techniqueis well known in the art, and described in for instance U.S. Pat. No.3,248,179 which is fully incorporated herein by reference. Thetemperature in the particle form process can be from about 85° C. toabout 110° C. Two example polymerization methods for the slurry processare those using a loop reactor and those utilizing a plurality ofstirred reactors in series, parallel, or combinations thereof.Non-limiting examples of slurry processes include continuous loop orstirred tank processes. Also, other examples of slurry processes aredescribed in U.S. Pat. No. 4,613,484, which is herein fully incorporatedby reference.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst, as a slurry in isohexane or as a dry freeflowing powder, is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isohexane containing monomer and optional comonomer.Hydrogen, optionally, may be added as a molecular weight control. (Inone embodiment hydrogen is added from 50 ppm to 500 ppm, such as from100 ppm to 400 ppm, such as 150 ppm to 300 ppm.)

The reactor may be maintained at a pressure of 2,000 kPa to 5,000 kPa,such as from 3,620 kPa to 4,309 kPa, and at a temperature of from about60° C. to about 120° C. depending on the desired polymer meltingcharacteristics. Reaction heat is removed through the loop wall sincemuch of the reactor is in the form of a double-jacketed pipe. The slurryis allowed to exit the reactor at regular intervals or continuously to aheated low pressure flash vessel, rotary dryer and a nitrogen purgecolumn in sequence for removal of the isohexane diluent and allunreacted monomer and comonomer. The resulting hydrocarbon free powderis then compounded for use in various applications.

Other additives may also be used in the polymerization, as desired, suchas one or more scavengers, promoters, modifiers, chain transfer agents(such as diethyl zinc), reducing agents, oxidizing agents, hydrogen,aluminum alkyls, or silanes.

Useful chain transfer agents are typically alkylalumoxanes, a compoundrepresented by the formula AlR₃, ZnR₂ (where each R is, independently, aC₁-C₈ hydrocarbyl, such as methyl, ethyl, propyl, butyl, penyl, hexyloctyl or an isomer thereof). Examples can include diethyl zinc,methylalumoxane, trimethylaluminum, triisobutylaluminum,trioctylaluminum, or a combination thereof.

Solution Polymerization

A solution polymerization is a polymerization process in which thepolymer is dissolved in a liquid polymerization medium, such as an inertsolvent or monomer(s) or their blends. A solution polymerization istypically homogeneous. A homogeneous polymerization is one where thepolymer product is dissolved in the polymerization medium. Such systemsare typically not turbid as described in Oliveira, J. V. et al. (2000)“High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems,”Ind. Eng. Chem. Res., v. 39, pp. 4627-4633. Generally solutionpolymerization involves polymerization in a continuous reactor in whichthe polymer formed and the starting monomer and catalyst materialssupplied, are agitated to reduce or avoid concentration gradients and inwhich the monomer acts as a diluent or solvent or in which a hydrocarbonis used as a diluent or solvent. Suitable processes typically operate attemperatures from about 0° C. to about 250° C., such as about 10° C. toabout 150° C., such as about 40° C. to about 140° C., such as about 50°C. to about 120° C., and at pressures of about 0.1 MPa or more, such as2 MPa or more. The upper pressure limit is not critically constrainedbut typically can be about 200 MPa or less, such as 120 MPa or less.Temperature control in the reactor can generally be obtained bybalancing the heat of polymerization and with reactor cooling by reactorjackets or cooling coils to cool the contents of the reactor, autorefrigeration, pre-chilled feeds, vaporization of liquid medium(diluent, monomers or solvent) or combinations of all three. Adiabaticreactors with pre-chilled feeds can also be used. The purity, type, andamount of solvent can be optimized for the maximum catalyst productivityfor a particular type of polymerization. The solvent can be alsointroduced as a catalyst carrier. The solvent can be introduced as a gasphase or as a liquid phase depending on the pressure and temperature.Advantageously, the solvent can be kept in the liquid phase andintroduced as a liquid. Solvent can be introduced in the feed to thepolymerization reactors.

Polyolefin Products

The present disclosure also provides compositions of matter which can beproduced by the processes described herein.

In at least one embodiment, a polyolefin is a propylene homopolymer, anethylene homopolymer or an ethylene copolymer, such aspropylene-ethylene and/or ethylene-alphaolefin (such as C₄ to C₂₀)copolymer (such as an ethylene-hexene copolymer or an ethylene-octenecopolymer). A polyolefin can have an Mw/Mn of greater than 1 to 4 (suchas greater than 1 to 3).

In at least one embodiment, a polyolefin is a homopolymer of ethylene orpropylene or a copolymer of ethylene such as a copolymer of ethylenehaving from 0.1 to 25 wt % (such as from 0.5 to 20 wt %, such as from 1to 15 wt %, such as from 5 to 17 wt %) of ethylene with the remainderbalance being one or more C₃ to C₂₀ olefin comonomers (such as C₃ to C₁₂alpha-olefin, such as propylene, butene, hexene, octene, decene,dodecene, such as propylene, butene, hexene, octene). A polyolefin canbe a copolymer of propylene such as a copolymer of propylene having from0.1 to 25 wt % (such as from 0.5 to 20 wt %, such as from 1 to 15 wt %,such as from 3 to 10 wt %) of propylene and from 99.9 to 75 wt % of oneor more of C₂ or C₄ to C₂₀ olefin comonomer (such as ethylene or C₄ toC₁₂ alpha-olefin, such as butene, hexene, octene, decene, dodecene, suchas ethylene, butene, hexene, octene).

In at least one embodiment, a polyolefin, such as a polypropylene (e.g.,iPP) or an ethylene-octene copolymer, has an Mw from 40,000 to1,500,000, such as from 70,000 to 1,000,000, such as from 90,000 to500,000, such as from 90,000 to 250,000, such as from 90,000 to 200,000,such as from 90,000 to 110,000.

In at least one embodiment, a polyolefin, such as a polypropylene (e.g.,iPP) or an ethylene-octene copolymer, has an Mn from 5,000 to 1,000,000,such as from 20,000 to 160,000, such as from 30,000 to 70,000, such asfrom 40,000 to 70,000. In at least one embodiment, a polyolefin, such asa polypropylene (e.g., iPP) or an ethylene-octene copolymer, has anMw/Mn value from 1 to 10, such as from 1.5 to 9, such as from 2 to 7,such as from 2 to 4, such as from 2.5 to 3, for example about 2.

In at least one embodiment, a polyolefin, such as a polypropylene (e.g.,iPP) or an ethylene-octene copolymer, has a melt temperature (Tm) offrom 100° C. to 150° C., such as 110° C. to 140° C., such as 120° C. to1350, such as 130° C. to 135° C.

In at least one embodiment, a polymer of the present disclosure has ag′_(vis) of greater than 0.9, such as greater than 0.92, such as greaterthan 0.95.

In at least one embodiment, the polymer is an ethylene copolymer, andthe comonomer is octene, at a comonomer content of from 1 wt % to 18 wt% octene, such as from 5 wt % to 15 wt %, such as from 8 wt % to 13 wt%, such as from 9 wt % to 12 wt %.

In at least one embodiment, the polymer produced herein has a unimodalor multimodal molecular weight distribution as determined by GelPermeation Chromatography (GPC). By “unimodal” is meant that the GPCtrace has one peak or inflection point. By “multimodal” is meant thatthe GPC trace has at least two peaks or inflection points. An inflectionpoint is that point where the second derivative of the curve changes insign (e.g., from negative to positive or vice versus).

In at least one embodiment, the polymer produced herein has acomposition distribution breadth index (CDBI) of 50% or more, such as60% or more, such as 70% or more. CDBI is a measure of the compositiondistribution of monomer within the polymer chains and is measured by theprocedure described in PCT publication WO 93/03093, published Feb. 18,1993, specifically columns 7 and 8 as well as in Wild, L. et al. (1982)“Determination of Branching Distributions in Polyethylene and ethyleneCopolymers,” J. Poly. Sci., Poly. Phys. Ed., v. 20, pp. 441-455, andU.S. Pat. No. 5,008,204, including that fractions having a weightaverage molecular weight (Mw) below 15,000 are ignored when determiningCDBI.

Copolymer of the present disclosure can have a reversed comonomer index.The reversed-co-monomer index (RCI,m) is computed from x2. (mol %co-monomer C₃, C₄, C₆, C₈, etc.), as a function of molecular weight,where x2 is obtained from the following expression in which n is thenumber of carbon atoms in the comonomer (3 for C₃, 4 for C₄, 6 for C₆,etc.):

${x\; 2} = {- {\frac{200\; w\; 2}{{{- 100}\; n} - {2\; w\; 2} + {{nw}\; 2}}.}}$

Then the molecular-weight distribution, W(z) where z=log₁₀ M, ismodified to W′(z) by setting to 0 the points in w that are less than 5%of the maximum of W; this is to effectively remove points for which theS/N in the composition signal is low. Also, points of W′ for molecularweights below 2000 gm/mole are set to 0. Then W′ is renormalized so that1=∫_(−∞) ^(∞) W′dzand a modified weight-average molecular weight (M_(w)′) is calculatedover the effectively reduced range of molecular weights as follows:M _(W)′=∫_(−∞) ^(∞)10^(z) *W′dz.The RCI,m is then computed as:RCI,m=∫ _(−∞) ^(∞) x2(10^(z) −M _(W)′)W′dz.

A reversed-co-monomer index (RCI,w) is also defined on the basis of theweight fraction co-monomer signal (w2/100) and is computed as follows:

${RCI},{w = {\int_{- \infty}^{\infty}{\frac{w\; 2}{100}\left( {10^{z} - M_{w}^{\prime}} \right)W^{\prime}{{dz}.}}}}$

Note that in the above definite integrals the limits of integration arethe widest possible for the sake of generality; however, in reality thefunction is only integrated over a finite range for which data isacquired, considering the function in the rest of the non-acquired rangeto be 0. Also, by the manner in which W′ is obtained, it is possiblethat W′ is a discontinuous function, and the above integrations need tobe done piecewise.

Three co-monomer distribution ratios are also defined on the basis ofthe % weight (w2) comonomer signal, denoted as CDR-1,w, CDR-2,w, andCDR-3,w, as follows:

${{CDR}\text{-}1},{w = \frac{w\; 2({Mz})}{w\; 2({Mw})}}$${{CDR}\text{-}2},{w = \frac{w\; 2({Mz})}{w\; 2\left( \frac{{Mw} + {Mn}}{2} \right)}}$${{CDR} - 3},{w = \frac{w\; 2\left( \frac{{Mz} + {Mw}}{2} \right)}{w\; 2\left( \frac{{Mw} + {Mn}}{2} \right)}}$where w2(Mw) is the % weight co-monomer signal corresponding to amolecular weight of Mw, w2(Mz) is the % weight co-monomer signalcorresponding to a molecular weight of Mz, w2[(Mw+Mn)/2)] is the %weight co-monomer signal corresponding to a molecular weight of(Mw+Mn)/2, and w2[(Mz+Mw)/2] is the % weight co-monomer signalcorresponding to a molecular weight of Mz+Mw/2, where Mw is theweight-average molecular weight, Mn is the number-average molecularweight, and Mz is the z-average molecular weight.

Accordingly, the co-monomer distribution ratios can be also definedutilizing the % mole co-monomer signal, CDR-1,m, CDR-2,m, CDR-3,m, as:

${{CDR}\text{-}1},{m = \frac{x\; 2({Mz})}{x\; 2({Mw})}}$${{CDR}\text{-}2},{m = \frac{x\; 2({Mz})}{x\; 2\left( \frac{{Mw} + {Mn}}{2} \right)}}$${{CDR}\text{-}3},{m = \frac{x\; 2\left( \frac{{Mz} + {Mw}}{2} \right)}{x\; 2\left( \frac{{Mw} + {Mn}}{2} \right)}}$where x2(Mw) is the % mole co-monomer signal corresponding to amolecular weight of Mw, x2(Mz) is the % mole co-monomer signalcorresponding to a molecular weight of Mz, x2[(Mw+Mn)/2)] is the % moleco-monomer signal corresponding to a molecular weight of (Mw+Mn)/2, andx2[(Mz+Mw)/2] is the % mole co-monomer signal corresponding to amolecular weight of Mz+Mw/2, where Mw is the weight-average molecularweight, Mn is the number-average molecular weight, and Mz is thez-average molecular weight.

In at least one embodiment of the present disclosure, the polymerproduced by the processes described herein includes ethylene and one ormore comonomers and the polymer has: 1) an RCI,m of 30 or more(alternatively from 30 to 250).

Molecular Weight, Comonomer Composition and Long Chain BranchingDetermination by Polymer Char GPC-IR Hyphenated with Multiple Detectors

The distribution and the moments of molecular weight (Mw, Mn, Mw/Mn,etc.), the comonomer content (C2, C3, C6, etc.) and the long chainbranching (g′) are determined by using a high temperature Gel PermeationChromatography (Polymer Char GPC-IR) equipped with a multiple-channelband-filter based Infrared detector IR5, an 18-angle light scatteringdetector and a viscometer. Three Agilent PLgel 10 μm Mixed-B LS columnsare used to provide polymer separation. Aldrich reagent grade1,2,4-trichlorobenzene (TCB) with 300 ppm antioxidant butylatedhydroxytoluene (BHT) is used as the mobile phase. The TCB mixture isfiltered through a 0.1 μm Teflon filter and degassed with an onlinedegasser before entering the GPC instrument. The nominal flow rate is1.0 mL/min and the nominal injection volume is 200 μL. The whole systemincluding transfer lines, columns, detectors are contained in an ovenmaintained at 145° C. Given amount of polymer sample is weighed andsealed in a standard vial with 80 μL flow marker (Heptane) added to it.After loading the vial in the autosampler, polymer is automaticallydissolved in the instrument with 8 mL added TCB solvent. The polymer isdissolved at 160° C. with continuous shaking for about 1 hour for mostPE samples or 2 hour for PP samples. The TCB densities used inconcentration calculation are 1.463 g/ml at room temperature and 1.284g/ml at 145° C. The sample solution concentration is from 0.2 to 2.0mg/ml, with lower concentrations being used for higher molecular weightsamples.

The concentration (c), at each point in the chromatogram is calculatedfrom the baseline-subtracted IR5 broadband signal intensity (I), usingthe following equation:c=βIwhere β is the mass constant determined with PE or PP standards. Themass recovery is calculated from the ratio of the integrated area of theconcentration chromatography over elution volume and the injection masswhich is equal to the pre-determined concentration multiplied byinjection loop volume.

The conventional molecular weight (IR MW) is determined by combininguniversal calibration relationship with the column calibration which isperformed with a series of monodispersed polystyrene (PS) standardsranging from 700 to 10M. The MW at each elution volume is calculatedwith following equation:

${\log\; M} = {\frac{\log\left( {K_{PS}/K} \right)}{a + 1} + {\frac{a_{PS} + 1}{a + 1}\log\; M_{PS}}}$where the variables with subscript “PS” stands for polystyrene whilethose without a subscript are for the test samples. In this method,a_(PS)=0.67 and K_(PS)=0.000175 while a and K are calculated asdescribed in the published in literature (Sun, T. et al. (2001) “Effectof Short Chain Branching on the Coil Dimensions of Polyolefins in DiluteSolutions,” Macromolecules, v. 34(19), pp. 6812-6820), except that forpurposes of this invention and claims thereto, α=0.695 and K=0.000579for linear ethylene polymers, α=0.705 and K=0.0002288 for polypropylene,α=0.695+(0.01*(wt. fraction propylene)) and K=0.000579-(0.0003502*(wt.fraction propylene)) for ethylene-propylene copolymers. Concentrationsare expressed in g/cm³, molecular weight is expressed in g/mole, andintrinsic viscosity (hence K in the Mark-Houwink equation) is expressedin dL/g unless otherwise noted.

The comonomer composition is determined by the ratio of the IR5 detectorintensity corresponding to CH₂ and CH₃ channel calibrated with a seriesof PE and PP homo/copolymer standards whose nominal value arepredetermined by NMR or FTIR such as EMCC commercial grades about LLDPE,Vistamaxx, ICP, etc.

The LS detector is the 18-angle Wyatt Technology High Temperature DAWNHELEOSII. The LS molecular weight (M) at each point in the chromatogramis determined by analyzing the LS output using the Zimm model for staticlight scattering (M. B. Huglin, Light Scattering from Polymer Solutions,Academic Press, 1971):

$\frac{K_{0}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theIR5 analysis, A₂ is the second virial coefficient. P(θ) is the formfactor for a monodisperse random coil, and K_(o) is the optical constantfor the system:

$K_{o} = \frac{4\;\pi^{2}{n^{2}\left( {{{dn}/d}\; c} \right)}^{2}}{\lambda^{4}N_{A}}$where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and λ=665 nm.

A high temperature Agilent (or Viscotek Corporation) viscometer, whichhas four capillaries arranged in a Wheatstone bridge configuration withtwo pressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(S), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the following equation:[η]=η_(S) /cwhere c is concentration and was determined from the IR5 broadbandchannel output. The viscosity MW at each point is calculated from thebelow equation:M=K _(PS) M ^(α) ^(PS) ⁺¹/[η].

The branching index (g′_(vis)) is calculated using the output of theGPC-IR5-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$where the summations are over the chromatographic slices, i, between theintegration limits. The branching index g′_(vis) is defined as:

$g_{vis}^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$M_(v) is the viscosity-average molecular weight based on molecularweights determined by LS analysis. The K/a are for the reference linearpolymers are as described above.

All the concentration is expressed in g/cm³, molecular weight isexpressed in g/mole, and intrinsic viscosity is expressed in dL/g unlessotherwise noted.

All molecular weights are reported in g/mol unless otherwise noted.

Differential Scanning Calorimetry (DSC-Procedure-2). MeltingTemperature, Tm, is measured by differential scanning calorimetry(“DSC”) using a DSCQ200 unit. The sample is first equilibrated at 25° C.and subsequently heated to 220° C. using a heating rate of 10° C./min(first heat). The sample is held at 220° C. for 3 min. The sample issubsequently cooled down to −100° C. with a constant cooling rate of 10°C./min (first cool). The sample is equilibrated at −100° C. before beingheated to 220° C. at a constant heating rate of 10° C./min (secondheat). The exothermic peak of crystallization (first cool) is analyzedusing the TA Universal Analysis software and the corresponding to 10°C./min cooling rate is determined. The endothermic peak of melting(second heat) is also analyzed using the TA Universal Analysis softwareand the peak melting temperature (Tm) corresponding to 10° C./minheating rate is determined. In the event of conflict between the DSCProcedure-1 and DSC procedure-2, DSC procedure-2 is used.

Blends

In another embodiment, the polymer (such as the polyethylene orpolypropylene) produced herein is combined with one or more additionalpolymers prior to being formed into a film, molded part or otherarticle. Other useful polymers include polyethylene, isotacticpolypropylene, highly isotactic polypropylene, syndiotacticpolypropylene, random copolymer of propylene and ethylene, and/orbutene, and/or hexene, polybutene, ethylene vinyl acetate, low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), highdensity polyethylene (HDPE), ethylene vinyl acetate, ethylene methylacrylate, copolymers of acrylic acid, polymethylmethacrylate or anyother polymers polymerizable by a high-pressure free radical process,polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins,ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer,styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH),polymers of aromatic monomers such as polystyrene, poly-1 esters,polyacetal, polyvinylidine fluoride, polyethylene glycols, and/orpolyisobutylene.

In at least one embodiment, the polymer (such as polyethylene orpolypropylene) is present in the above blends, at from 10 to 99 wt %,based upon the weight of the polymers in the blend, such as 20 to 95 wt%, such as at least 30 to 90 wt %, such as at least 40 to 90 wt %, suchas at least 50 to 90 wt %, such as at least 60 to 90 wt %, such as atleast 70 to 90 wt %.

The blends described above may be produced by mixing the polymers of thepresent disclosure with one or more polymers (as described above), byconnecting reactors together in series to make reactor blends or byusing more than one catalyst in the same reactor to produce multiplespecies of polymer. The polymers can be mixed together prior to beingput into the extruder or may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, suchas by dry blending the individual components and subsequently meltmixing in a mixer, or by mixing the components together directly in amixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabenderinternal mixer, or a single or twin-screw extruder, which may include acompounding extruder and a side-arm extruder used directly downstream ofa polymerization process, which may include blending powders or pelletsof the resins at the hopper of the film extruder. Additionally,additives may be included in the blend, in one or more components of theblend, and/or in a product formed from the blend, such as a film, asdesired. Such additives are well known in the art, and can include, forexample: fillers; antioxidants (e.g., hindered phenolics such asIRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites(e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives;tackifiers, such as polybutenes, terpene resins, aliphatic and aromatichydrocarbon resins, alkali metal and glycerol stearates, andhydrogenated rosins; UV stabilizers; heat stabilizers; anti-blockingagents; release agents; anti-static agents; pigments; colorants; dyes;waxes; silica; fillers; and talc.

Films

One or more of the foregoing polymers, such as the foregoingpolyethylenes, polypropylenes, or blends thereof, may be used in avariety of end-use applications. Such applications include, for example,mono- or multi-layer blown, extruded, and/or shrink films. These filmsmay be formed by any number of well-known extrusion or coextrusiontechniques, such as a blown bubble film processing technique, whereinthe composition can be extruded in a molten state through an annular dieand then expanded to form a uni-axial or biaxial orientation melt priorto being cooled to form a tubular, blown film, which can then be axiallyslit and unfolded to form a flat film. Films may be subsequentlyunoriented, uniaxially oriented, or biaxially oriented to the same ordifferent extents. One or more of the layers of the film may be orientedin the transverse and/or longitudinal directions to the same ordifferent extents. The uniaxially orientation can be accomplished usingtypical cold drawing or hot drawing methods. Biaxial orientation can beaccomplished using tenter frame equipment or a double bubble processesand may occur before or after the individual layers are broughttogether. For example, a polyethylene layer can be extrusion coated orlaminated onto an oriented polypropylene layer or the polyethylene andpolypropylene can be coextruded together into a film then oriented.Likewise, oriented polypropylene could be laminated to orientedpolyethylene or oriented polyethylene could be coated onto polypropylenethen optionally the combination could be oriented even further.Typically the films are oriented in the Machine Direction (MD) at aratio of up to 15, such as between 5 and 7, and in the TransverseDirection (TD) at a ratio of up to 15, such as 7 to 9. However, in atleast one embodiment the film is oriented to the same extent in both theMD and TD directions.

The films may vary in thickness depending on the intended application;however, films of a thickness from 1 μm to 50 μm are usually suitable.Films intended for packaging are usually from 10 μm to 50 μm thick. Thethickness of the sealing layer is typically 0.2 μm to 50 μm. There maybe a sealing layer on both the inner and outer surfaces of the film orthe sealing layer may be present on only the inner or the outer surface.

In at least one embodiment, one or more layers may be modified by coronatreatment, electron beam irradiation, gamma irradiation, flametreatment, or microwave. In at least one embodiment, one or both of thesurface layers is modified by corona treatment.

This invention further relates to:

-   P1. A process to produce an activator compound comprising:

i) contacting a compound according to formula (A) with a compound havingthe general formula M-(BR⁴R⁵R⁶R⁷) in an aliphatic hydrocarbon solvent,an alicyclic hydrocarbon solvent, or a combination thereof, at areaction temperature and for a period of time sufficient to produce amixture comprising the activator compound according to formula (I) and asalt having the formula M(X);

-   -   wherein formula (A) is represented by:

-   -   wherein formula (I) is represented by:

-   -   wherein in each of formulae (A) and (I):        -   each of R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independently a            hydrogen or a C₁-C₄₀ linear alkyl;        -   R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² together comprise 15 or            more carbon atoms;        -   each of R⁴, R⁵, R⁶, and R⁷ comprises an aromatic hydrocarbon            having from 6 to 24 carbon atoms;        -   at least one of R⁴, R⁵, R⁶, and R⁷ is substituted with one            or more fluorine atoms;        -   X is halogen; and        -   M is a Group 1 metal;        -   wherein at least one of R⁸, R⁹, R¹⁰, R¹¹, and R¹² is            preferably not hydrogen; and wherein a 1 millimole per liter            mixture of the activator compound in n-hexane, isohexane,            cyclohexane, methylcyclohexane, or a combination thereof,            forms a clear homogeneous solution at 25° C.

-   P2. The process according to paragraph P1, wherein at least one of    R⁴, R⁵, R⁶, and R⁷ comprises a perfluoro substituted phenyl moiety,    a perfluoro substituted naphthyl moiety, a perfluoro substituted    biphenyl moiety, a perfluoro substituted triphenyl moiety, or a    combination thereof.

-   P3. The process according to paragraph P1 or P2, wherein R⁴, R⁵, R⁶,    and R⁷ are perfluoro substituted phenyl radicals and R² is not a    C₁-C₄₀ linear alkyl.

-   P4. The process according to any one of paragraphs P1 through P3,    wherein R⁴, R⁵, R⁶, and R⁷ are perfluoro substituted naphthyl    radicals.

-   P5. The process according to any one of paragraphs P1 through P4,    wherein R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² together comprise 20 or    more carbon atoms.

-   P6. The process according to any one of paragraphs P1 through P5,    wherein R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² together comprise 30 or    more carbon atoms.

-   P7. The process according to any one of paragraphs P1 through P6,    wherein two of more of R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² are each a    C₁₀-C₄₀ linear alkyl radical.

-   P8. The process according to any one of paragraphs P1 through P7,    wherein two or more of R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² are each a    C₁₀-C₂₂ linear alkyl radical.

-   P9. The process according to any one of paragraphs P1 through P8,    wherein two or more of R¹, R², and R¹⁰ are each a C₁₀-C₄₀ linear    alkyl and R⁸ and R¹² are hydrogen.

-   P10. The process according to any one of paragraphs P1 through P9,    wherein two or more of R¹, R², and R¹⁰ are each a C₁₀-C₂₂ linear    alkyl and R⁸ and R¹² are hydrogen.

-   P11. The process according to any one of paragraphs P1 through P10,    wherein at least one of R⁸, R⁹, R¹⁰, R¹¹, and R¹² is a linear alkyl    radical comprising 6 or more carbon atoms.

-   P12. The process according to any one of paragraphs P1 through P11,    wherein R⁸ and R¹² are hydrogen and R¹⁰ is a linear alkyl radical    comprising 6 or more carbon atoms.

-   P13. The process according to any one of paragraphs P1 through P12,    wherein R¹ is methyl and each of R² and R¹⁰ is C₆-C₄₀ linear alkyl    radical.

-   P14. The process according to any one of paragraphs P1 through P13,    further comprising the step of filtering the mixture to remove the    salt to produce a clear homogeneous solution comprising the    activator compound according to formula (I) and optionally removing    at least a portion of the solvent.

-   P15. The process according to any one of paragraphs P1 through P14,    wherein the reaction temperature is less than or equal to the reflux    temperature of the solvent at atmospheric pressure and the time is    less than or equal to about 24 hours.

-   P16. The process according to any one of paragraphs P1 through P15,    wherein the reaction temperature is from about 20° C. to less than    or equal to about 50° C., and the time is less than or equal to    about 2 hours.

-   P17. The process according to any one of paragraphs P1 through P16,    wherein the solvent is hexane, isohexane, cyclohexane,    methylcyclohexane, or a combination thereof.

-   P18. The process according to any one of paragraphs P1 through P17,    wherein a 5 millimole per liter mixture of the activator compound in    n-hexane, isohexane, cyclohexane, methylcyclohexane, or a    combination thereof, forms a clear homogeneous solution at 25° C.

-   P19. The process according to any one of paragraphs P1 through P18,    wherein a 10 millimole per liter mixture of the activator compound    in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a    combination thereof, forms a clear homogeneous solution at 25° C.

-   P20. The process according to any one of paragraphs P1 through P19,    wherein a 20 millimole per liter mixture of the activator compound    in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a    combination thereof, forms a clear homogeneous solution at 25° C.

-   P21. A catalyst system comprising a catalyst and the activator    compound according to any one of paragraphs P1 through P20.

-   P22. A catalyst system comprising a catalyst and the activator    compound represented by formula (I):

-   -   produced by contacting a compound according to formula (A) with        a compound having the general formula M-(BR⁴R⁵R⁶R⁷) in an        aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent,        or a combination thereof, at a reaction temperature and for a        period of time sufficient to produce a mixture comprising the        activator compound according to formula (I) and a salt having        the formula M(X);    -   wherein formula (A) is represented by:

-   -   wherein for formula (I) and formula (A):        -   each of R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independently a            hydrogen or a C₁-C₄₀ linear alkyl;        -   R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² together comprise 15 or            more carbon atoms;        -   each of R⁴, R⁵, R⁶, and R⁷ comprises an aromatic hydrocarbon            having from 6 to 24 carbon atoms;        -   at least one of R⁴, R⁵, R⁶, and R⁷ is substituted with one            or more fluorine atoms; X is halogen; and        -   M is a Group 1 metal; wherein at least one of R⁸, R⁹, R¹⁰,            R¹¹, and R¹² is not hydrogen; and    -   wherein a 1 millimole per liter mixture of the activator        compound (I) in n-hexane, isohexane, cyclohexane,        methylcyclohexane, or a combination thereof, forms a clear        homogeneous solution at 25° C.

-   P23. The catalyst system according to paragraph P21 or P22, further    comprising a support material.

-   P24. The catalyst system according to any one of paragraphs P21    through P23, wherein the catalyst is represented by formula (II) or    formula (III):

-   -   wherein in each of formula (II) and formula (III):        -   M is the metal center, and is a Group 4 metal;        -   n is 0 or 1;        -   T is an optional bridging group selected from dialkylsilyl,            diarylsilyl, dialkylmethyl, ethylenyl or            hydrocarbylethylenyl wherein one, two, three or four of the            hydrogen atoms in ethylenyl are substituted by hydrocarbyl;        -   Z is nitrogen, oxygen, sulfur, or phosphorus (preferably            nitrogen); q is 1 or 2 (preferably q is 1 when Z in N);        -   R′ is a C₁-C₄₀ alkyl or substituted alkyl group, preferably            a linear C₁-C₄₀ alkyl or substituted alkyl group;        -   X₁ and X₂ are, independently, hydrogen, halogen, hydride            radicals, hydrocarbyl radicals, substituted hydrocarbyl            radicals, halocarbyl radicals, substituted halocarbyl            radicals, silylcarbyl radicals, substituted silylcarbyl            radicals, germylcarbyl radicals, or substituted germylcarbyl            radicals; or both X₁, and X₂ are joined and bound to the            metal atom to form a metallacycle ring containing from about            3 to about 20 carbon atoms; or both together can be an            olefin, diolefin or aryne ligand.

-   P25. The catalyst system according to any one of paragraphs P21    through P24, wherein the catalyst is one or more of:

-   bis(1-methyl, 3-n-butyl cyclopentadienyl) M(R)₂;

-   dimethylsilyl bis(indenyl)M(R)₂;

-   bis(indenyl)M(R)₂;

-   dimethylsilyl bis(tetrahydroindenyl)M(R)₂;

-   bis(n-propylcyclopentadienyl)M(R)₂;

-   dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M(R)₂;

-   dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)M(R)₂;

-   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M(R)₂;

-   dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)M(R)₂;

-   μ-(CH₃)₂Si(cyclopentadienyl)(1-adamantylamido)M(R)₂;

-   μ-(CH₃)₂Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M(R)₂;

-   μ-(CH₃)₂(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;

-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;

-   μ-(CH₃)₂C(tetramethylcyclopentadienyl)(1-adamantylamido)M(R)₂;

-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M(R)₂;

-   μ-(CH₃)₂Si(fluorenyl)(1-tertbutylamido)M(R)₂;

-   μ-(CH₃)₂Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂;

-   μ-(C₆H₅)₂C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)₂;

-   μ-(CH₃)₂Si(η⁵-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)M(R)₂;    -   where M is selected from Ti, Zr, and Hf; and R is selected from        halogen or C₁ to C₅ alkyl.

-   P26. A process of polymerizing olefins to produce at least one    polyolefin, the process comprising contacting at least one olefin    with the catalyst system according to any one of paragraphs P21    through P25 and obtaining a polyolefin.

-   P27. A process of polymerizing olefins to produce at least one    polyolefin, the process comprising:    -   i) contacting a compound according to formula (A) with a        compound having the general formula M-(BR⁴R⁵R⁶R⁷) in an        aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent,        or a combination thereof, at a reaction temperature and for a        period of time sufficient to produce a mixture comprising an        activator compound according to formula (I) and a salt having        the formula M(X);    -   wherein formula (A) is represented by:

-   -   wherein formula (I) is represented by:

-   -   wherein in each of formulae (A) and (I):        -   each of R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independently a            hydrogen or a C₁-C₄₀ linear alkyl;        -   R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² together comprise 15 or            more carbon atoms;        -   each of R⁴, R⁵, R⁶, and R′ comprises an aromatic hydrocarbon            having from 6 to 24 carbon atoms;        -   at least one of R⁴, R⁵, R⁶, and R′ is substituted with one            or more fluorine atoms;        -   X is halogen; and        -   M is a Group 1 metal;    -   wherein at least one of R⁸, R⁹, R¹⁰, R¹¹, and R¹² is not        hydrogen;    -   ii) filtering the mixture to remove the salt to produce a clear        homogeneous solution comprising the activator compound according        to formula (I) and optionally removing at least a portion of the        solvent;    -   iii) combining the activator and a catalyst to form a catalyst        system, and    -   iv) contacting at least one olefin with the catalyst system and        obtaining the polyolefin; wherein a 1 millimole per liter        mixture of the activator compound in n-hexane, isohexane,        cyclohexane, methylcyclohexane, or a combination thereof, forms        a clear homogeneous solution at 25° C.

-   P28. The process according to paragraph P26 or P27, wherein the at    least one olefin is propylene and the polyolefin is isotactic    polypropylene.

-   P29. A process of polymerizing olefins to produce at least one    polyolefin, the process comprising contacting two or more different    olefins with the catalyst system according to any one of paragraphs    P21 through P25 and obtaining a polyolefin.

-   P30. The process of any one of paragraphs P26 through P29, wherein    the two or more olefins are ethylene and propylene.

-   P31. The process of any one of paragraphs P26 through P30, wherein    the two or more olefins further comprise a diene.

-   P32. A solution comprising the compound the catalyst system of any    of paragraphs P21 through P26 and an aliphatic solvent where    aromatic solvents are absent.

-   P33. The process of any of paragraphs P1 through P20 or P27 through    P31 where aromatic solvents are absent.

-   P34. A composition comprising the catalyst system of paragraph P23    and an aliphatic solvent, where aromatic solvents are absent.

EXAMPLES

Lithium tetrakis(pentafluorophenyl)borate etherate (Li—BF20) waspurchased from Boulder Scientific. N,N-dimethylaniliniumtetrakis(heptafluoronaphthalen-2-yl)borate (DMAH-BF28) was purchasedfrom Grace Davison and converted to sodiumtetrakis(heptafluoronaphthalen-2-yl)borate (Na—BF28) by reaction withsodium hydride in toluene. n-Hexane was purchased from Sigma-Aldrich.Isohexane was purchased from South Hampton Resources.

N-methyl-4-nonadecyl-N-octadecylanilinum chloride salt was synthesizedas previously reported. NMR spectra were recorded on a Bruker 500 or 400NMR with chemical shifts referenced to residual solvent peaks (CDCl₃:7.27 ppm for ¹H, 77.23 ppm for ¹³C).

The activators were produced according to the following reaction underthe conditions specified.

Synthesis of N-methyl-4-nonadecyl-N-octadecylbenzenaminium-BF20 inisohexane

A slurry of N-methyl-4-nonadecyl-N-octadecylanilinum chloride (1.50 g,2.26 mmol) and Li—BF20 (1.72 g, 2.26 mmol) in 100 mL of isohexane washeated at reflux for 1.5 hours. Once cooled to ambient temperature, themixture was filtered. The filtrate was concentrated to give the productas a colorless oil in 61% yield.

Synthesis of N-methyl-4-nonadecyl-N-octadecylbenzenaminium-BF28 inn-hexane

A slurry of N-methyl-4-nonadecyl-N-octadecylanilinum chloride (2.00 g,3.02 mmol) and Na—BF28 (3.16 g, 3.02 mmol) in 100 mL of n-hexane washeated at reflux for 1.5 hours. Once cooled to ambient temperature, themixture was filtered. The filtrate was concentrated to give the productas a brown oil in 90% yield.

Synthesis of N-methyl-4-nonadecyl-N-octadecylbenzenaminium-BF28 inisohexane

A slurry of N-methyl-4-nonadecyl-N-octadecylanilinum chloride (1.89 g,2.85 mmol) and Na—BF28 (2.98 g, 2.85 mmol) in 100 mL of isohexane washeated at reflux for 1.5 hours. Once cooled to ambient temperature, themixture was filtered. The filtrate was concentrated to give the productas a brown oil in quantitative yield.

Synthesis of N-methyl-4-nonadecyl-N-octadecylbenzenaminium-BF28 inisohexane

A slurry of N-methyl-4-nonadecyl-N-octadecylanilinum chloride (1.89 g,2.85 mmol) and Na—BF28 (2.98 g, 2.85 mmol) in 100 mL of isohexane wasstirred at room temperature for 1.5 hours. The mixture was filtered, andthe filtrate was concentrated to give the product as a brown oil inquantitative yield.

FIG. 1 shows a comparison of ¹H NMR spectra of NOMAH-BF₂₈ activatorsprepared in n-hexane and cyclohexane.

FIG. 2 shows a comparison of ¹¹B NMR spectrum of NOMAH-BF₂₈ ofNOMAH-BF₂₈ activators prepared in n-hexane and cyclohexane.

FIG. 3 shows an activity comparison of comparative activators in tolueneand in methylcyclohexane. As these data show, the dimethyl ammoniumactivators have essentially no activity in non-aromatic solvents.

Polymerization in Parallel Pressure Reactor

Solvents used were polymerization-grade toluene, and isohexane suppliedby ExxonMobil Chemical Company and purified by passing through a seriesof columns: two 500 cc Oxyclear cylinders in series from Labclear(Oakland, Calif.), followed by two 500 cc columns in series packed withdried 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company), and two 500cc columns in series packed with dried 5 Å mole sieves (8-12 mesh;Aldrich Chemical Company). 1-octene (C₈) and 1-hexene (C6) (98%, AldrichChemical Company) were dried by stirring over NaK overnight followed byfiltration through basic alumina (Aldrich Chemical Company, BrockmanBasic 1).

Polymerization-grade ethylene (C₂) was used and further purified bypassing the gas through a series of columns: 500 cc Oxyclear cylinderfrom Labclear (Oakland, Calif.) followed by a 500 cc column packed withdried 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company) and a 500 cccolumn packed with dried 5 Å mole sieves (8-12 mesh; Aldrich ChemicalCompany).

Polymerization grade propylene (C₃) was used and further purified bypassing it through a series of columns: 2250 cc Oxiclear cylinder fromLabclear followed by a 2250 cc column packed with 3 Å mole sieves (8-12mesh; Aldrich Chemical Company), then two 500 cc columns in seriespacked with 5 Å mole sieves (8-12 mesh; Aldrich Chemical Company), thena 500 cc column packed with Selexsorb CD (BASF), and finally a 500 cccolumn packed with Selexsorb COS (BASF).

Solutions of the metal complexes and activators were prepared in adrybox using toluene or methylcyclohexane. Concentrations were typically0.2 mmol/L. Tri-n-octylaluminum (TNOAL, neat, AkzoNobel) was typicallyused as a scavenger. Concentration of the TNOAL solution in tolueneranged from 0.5 to 2.0 mmol/L.

Polymerizations were carried out in a parallel pressure reactor, asgenerally described in U.S. Pat. Nos. 6,306,658; 6,455,316; 6,489,168;WO 00/09255; and Murphy, V. et al. (2003) “A Fully IntegratedHigh-Throughput Screening Methodology for the Discovery of NewPolyolefin Catalysts: Discovery of a New Class of High TemperatureSingle-Site Group (IV) Copolymerization Catalysts,” J. Am. Chem. Soc.,v. 125, pp. 4306-4317, each of which is fully incorporated herein byreference. The experiments were conducted in an inert atmosphere (N₂)drybox using autoclaves equipped with an external heater for temperaturecontrol, glass inserts (internal volume of reactor=23.5 mL for C₂ andC₂/C; 22.5 mL for C₃ runs), septum inlets, regulated supply of nitrogen,ethylene and propylene, and equipped with disposable PEEK mechanicalstirrers (800 RPM). The autoclaves were prepared by purging with drynitrogen at 110° C. or 115° C. for 5 hours and then at 25° C. for 5hours. Although the specific quantities, temperatures, solvents,reactants, reactant ratios, pressures, and other variables arefrequently changed from one polymerization run to the next, thefollowing describes a typical polymerization performed in a parallelpressure reactor.

Catalyst systems dissolved in solution were used in the polymerizationexamples below, unless specified otherwise.

Ethylene-Octene Copolymerization (EO).

A pre-weighed glass vial insert and disposable stirring paddle werefitted to each reaction vessel of the reactor, which contains 48individual reaction vessels. The reactor was then closed and purged withethylene. Each vessel was charged with enough solvent (typicallyisohexane) to bring the total reaction volume, including the subsequentadditions, to the desired volume, typically 5 mL. 1-octene, if required,was injected into the reaction vessel and the reactor was heated to theset temperature and pressurized to the predetermined pressure ofethylene, while stirring at 800 rpm. The aluminum compound (such astri-n-octylaluminum) in toluene was then injected as scavenger followedby addition of the activator solution (typically 1.0-1.2 molarequivalents).

The catalyst (and activator solutions for Run A) were all prepared intoluene. The catalyst solution (typically 0.020-0.080 μmol of metalcomplex) was injected into the reaction vessel and the polymerizationwas allowed to proceed until a pre-determined amount of ethylene (quenchvalue typically 20 psi) had been used up by the reaction. Alternatively,the reaction may be allowed to proceed for a set amount of time (maximumreaction time typically 30 minutes). Ethylene was added continuously(through the use of computer controlled solenoid valves) to theautoclaves during polymerization to maintain reactor gauge pressure (Psetpt, +/−2 psig) and the reactor temperature (T) was monitored andtypically maintained within +/−1° C. The reaction was quenched bypressurizing the vessel with compressed air. After the reactor wasvented and cooled, the glass vial insert containing the polymer productand solvent was removed from the pressure cell and the inert atmosphereglove box, and the volatile components were removed using a GenevacHT-12 centrifuge and Genevac VC3000D vacuum evaporator operating atelevated temperature and reduced pressure. The vial was then weighed todetermine the yield of the polymer product. The resultant polymer wasanalyzed by Rapid GPC as described herein to determine the molecularweight; by FT-IR as described herein to determine percent octeneincorporation; and by DSC as described herein to determine melting point(T_(m)).

Equivalence is determined based on the mole equivalents relative to themoles of the transition metal in the catalyst complex.

Polymer Characterization.

Polymer sample solutions were prepared by dissolving polymer in1,2,4-trichlorobenzene (TCB, 99+% purity from Sigma-Aldrich) containing2,6-di-tert-butyl-4-methylphenol (BHT, 99% from Aldrich) at 165° C. in ashaker oven for approximately 3 hours. The typical concentration ofpolymer in solution was between 0.1 to 0.9 mg/mL with a BHTconcentration of 1.25 mg BHT/mL of TCB.

To determine various molecular weight related values by GPC, hightemperature size exclusion chromatography was performed using anautomated “Rapid GPC” system as generally described in U.S. Pat. Nos.6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632;6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is fullyincorporated herein by reference. This apparatus has a series of three30 cm×7.5 mm linear columns, each containing PLgel 10 μm, Mix B. The GPCsystem was calibrated using polystyrene standards ranging from 580 to3,390,000 g/mol. The system was operated at an eluent flow rate of 2.0mL/minutes and an oven temperature of 165° C. 1,2,4-trichlorobenzene wasused as the eluent. The polymer samples were dissolved in1,2,4-trichlorobenzene at a concentration of 0.28 mg/mL and 400 uL of apolymer solution was injected into the system. The concentration of thepolymer in the eluent was monitored using an evaporative lightscattering detector. The molecular weights presented are relative tolinear polystyrene standards and are uncorrected, unless indicatedotherwise.

Differential Scanning Calorimetry (DSC) measurements were performed on aTA-Q100 instrument to determine the melting point (T_(m)) of thepolymers. Samples were pre-annealed at 220° C. for 15 minutes and thenallowed to cool to room temperature overnight. The samples were thenheated to 220° C. at a rate of 100° C./min and then cooled at a rate of50° C./min. Melting points were collected during the heating period.

The weight percent of ethylene incorporated in polymers was determinedby rapid FT-IR spectroscopy on a Bruker Equinox 55+IR in reflectionmode. Samples were prepared in a thin film format by evaporativedeposition techniques. FT-IR methods were calibrated using a set ofsamples with a range of known wt % ethylene content. Forethylene-1-octene copolymers, the wt % octene in the copolymer wasdetermined via measurement of the methyl deformation band at ˜1375 cm⁻¹.The peak height of this band was normalized by the combination andovertone band at ˜4321 cm⁻¹, which corrects for path length differences.

Ethylene-Octene Copolymerization (EO).

A series of ethylene-octene polymerizations were performed in theparallel pressure reactor according to the procedure described above. Inthese studies rac-dimethylsilyl-bis(indenyl)hafnium dimethyl (MCN-1) wasused as the catalyst along with the indicated ammonium borate activator.In a typical experiment, an automated syringe was used to introduce thefollowing reagents, if utilized, into the reactor in the followingorder: isohexane (0.50 mL), 1-octene (100 μL), additional isohexane(0.50 mL), an isohexane solution of TNOAL scavenger (0.005 M, 100 μL),additional isohexane (0.50 mL), a toluene solution of the respectivepolymerization catalyst (110 μL, 0.2 mM), additional isohexane (0.50mL), a solution of the respective activator (110 μL, 0.2 mM), thenadditional isohexane so that the total solvent volume for each run was 5mL. Catalyst and activator were used in a 1:1.1 ratio. Each reaction wasperformed at a specified temperature range between 50 and 120° C.,typically 80° C., while applying about 75 psig of ethylene (monomer)gas. Each reaction was allowed to run for about 20 minutes (˜1,200seconds) or until approximately 20 psig of ethylene gas uptake wasobserved, at which point the reactions were quenched with air (˜300psig). When sufficient polymer yield was attained (e.g., at least ˜10mg), the polyethylene product was analyzed by Rapid GPC as describedherein. Experimental conditions and data are reported in Table 3, wherethe general conditions were MCN-1=20 nmol; activator=2.2 nmol;1-octene=100 μL; solvent=isohexane; total volume=5 mL;tri(n-octyl)aluminum=500 nmol; T=80° C.

TABLE 3 Data for the ethylene-octene copolymerization. yield timeactivity T_(m) % Example Activator (mg) (s) (kg/mmol/h) Mw Mn PDI (° C.)octene Comparative 1 DMAH-BF20 92 25.7 644.4 362,472 189,698 1.91 37.558.6 Comparative2  DMAH-BF20 75 26.5 509.4 371,373 213,514 1.74 35.442.3 3 NOMAH-BF20 90 37.6 430.9 413,270 207,838 1.99 33.9 46.7 4NOMAH-D4 75 32.6 414.1 420,680 245,773 1.71 37.4 44.9 5 NOMAH-D4 71 26.7478.7 411,768 223,321 1.84 32.6 45.6 6 NOMAH-D4 71 31.2 409.6 393,303209,625 1.88 36.1 43.7

Ethylene Homopolymerization (PE).

A series of ethylene polymerizations were performed in the parallelpressure reactor according to the procedure described above. In theseexamples rac-dimethylsilyl-bis(indenyl)hafnium dimethyl (MCN-1) was usedas the catalyst along with ammonium borate activators. In a typicalexperiment an automated syringe was used to introduce the followingreagents, if utilized, into the reactor in the following order:isohexane (0.50 mL), an isohexane solution of TNOAL scavenger (0.005 M,60 μL), additional isohexane (0.50 mL), a solution of the respectivepolymerization catalyst (110 μL, 0.2 mM), additional isohexane (0.50mL), a solution of the respective activator (110 μL, 0.2 mM), thenadditional isohexane so that the total solvent volume for each run was 5mL. Catalyst and activator were used in a 1:1.1 ratio. Each reaction wasperformed at a specified temperature range between 50 and 120° C.,typically 80° C., while applying about 75 psig of ethylene (monomer)gas. Each reaction was allowed to run for about 20 minutes (˜1,200seconds) or until approximately 20 psig of ethylene gas uptake wasobserved, at which point the reactions were quenched with air (˜300psig). When sufficient polymer yield was attained (e.g., at least ˜10mg), the polyethylene product was analyzed by Rapid GPC, describedbelow. Run conditions and data are reported in Table 4 where the generalconditions were: MCN-1=20 nmol; activator=2.2 nmol; solvent=isohexane;total volume=5 mL; tri(n-octyl)aluminum=500 nmol; T=80° C.

TABLE 4 Data for ethylene homopolymerization. yield time activity T_(m)Example activator (mg) (s) (kg/mmol/h) Mw Mn PDI (° C.) Comparative 7DMAH-BF20 68 42.4 288.7 875,463 431,174 2.03 135.2 Comparative 8DMAH-BF20 57 25.2 407.1 663,329 336,644 1.97 135.1 9 NOMAH-BF20 70 58.5215.4 847,700 412,612 2.05 135.6 10 NOMAH-BF20 64 48.5 237.5 740,474365,330 2.03 135.6 11 NOMAH-BF20 59 26.6 399.2 759,613 467,750 1.62135.3 12 NOMAH-BF20 58 30.7 340.1 728,453 418,731 1.74 135.6

Propylene Homopolymerization (PP).

The parallel pressure reactor was prepared as described above and purgedwith propylene. In these polymerization examples, the metallocene usedas the catalyst was again rac-dimethylsilyl-bis(indenyl)hafnium dimethyl(MCN-1) along with the indicated ammonium borate activators. A solutionof the activators was prepared. Isohexane was then injected into eachvessel at room temperature followed by a predetermined amount ofpropylene gas. The reactor was heated to the set temperature whilestirring at 800 rpm, and the scavenger, activator and catalyst solutionswere injected sequentially to each vessel. The polymerization wasallowed to proceed as described previously. These data are presented inTable 5, wherein the general conditions were: MCN-1=20 nmol;activator=22 nmol; solvent=isohexane; total volume=5 mL;tri(n-octyl)aluminum=500 nmol; T=100° C.; P=160 PSI.

TABLE 5 Data for homopolymerization of propylene. yield time activityT_(m) Example activator (mg) (s) (kg/mmol/h) Mw Mn PDI (° C.)Comparative 13 DMAH-BF20 28 1200.9 4.2 48,236 29,484 1.64 116.3Comparative 14 DMAH-BF20 71 1200.2 10.6 51,203 30,477 1.68 115.5 15NOMAH-BF20 66 1200.7 9.9 44,663 27,207 1.64 113.8 16 NOMAH-BF20 75 18772.2 45,223 26,385 1.71 114.2 17 NOMAH-BF20 15 1201.4 2.2 61,591 35,6371.73 121.7

The NOMAH-BF20 activator prepared using isohexane was tested forpolymerization activity using parallel pressure reactors. Theactivator/catalyst system disclosed provided EO copolymers of sufficientmolecular weight and octane incorporation. Equally, polyethylenepolymers produced were equivalent to those of the control conditions.

As these data show, activators, catalyst systems, and processes of thepresent disclosure can provide improved solubility in aliphaticsolvents, as compared to conventional activator compounds and catalystsystems.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the present disclosure have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe present disclosure. Accordingly, it is not intended that the presentdisclosure be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including.” Likewise whenever acomposition, an element or a group of elements is preceded with thetransitional phrase “comprising,” it is understood that we alsocontemplate the same composition or group of elements with transitionalphrases “consisting essentially of,” “consisting of,” “selected from thegroup of consisting of,” or “is” preceding the recitation of thecomposition, element, or elements and vice versa.

We claim:
 1. A process to produce an activator compound comprising: i)contacting a compound according to formula (A) with a compound havingthe general formula M-(BR4R5R6R7) in a solvent including isohexane,hexane, or n-hexane, or a combination thereof, at a reaction temperatureranging from 30° C. to 20° C., and for a period of time sufficient toproduce a mixture comprising the activator compound according to formula(I) and a salt having the formula M(X); wherein formula (A) isrepresented by:

wherein formula (I) is represented by:

wherein in each of formulae (A) and (I): each of R¹ and R² isindependently a hydrogen or a C₁-C₄₀ linear alkyl, with R⁸, R⁹, R¹⁰,R¹¹, and R¹² being independently C₁-C₄₀ linear alkyl and not hydrogen;R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² together comprise 15 or more carbonatoms; each of R⁴, R⁵, R⁶, and R⁷ comprises an aromatic hydrocarbonhaving from 6 to 24 carbon atoms; at least one of R⁴, R⁵, R⁶, and R⁷ issubstituted with one or more fluorine atoms; X is halogen; and M is aGroup 1 metal; and wherein a 1 millimole per liter mixture of theactivator compound in n-hexane, isohexane, hexane, or a combinationthereof, forms a clear homogeneous solution at 25° C.
 2. The process ofclaim 1, wherein at least one of R⁴, R⁵, R⁶, and R⁷ comprises aperfluoro substituted phenyl moiety, a perfluoro substituted naphthylmoiety, a perfluoro substituted biphenyl moiety, a perfluoro substitutedtriphenyl moiety, or a combination thereof.
 3. The process of claim 1,wherein R⁴, R⁵, R⁶, and R⁷ are perfluoro substituted phenyl radicals andR² is not a C₁-C₄₀ linear alkyl.
 4. The process of claim 1, wherein R⁴,R⁵, R⁶, and R⁷ are perfluoro substituted naphthyl radicals.
 5. Theprocess of claim 1, wherein R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² togethercomprise 20 or more carbon atoms.
 6. The process of claim 1, wherein R¹,R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² together comprise 30 or more carbon atoms.7. The process of claim 1, wherein two of more of R¹, R², R⁸, R⁹, R¹⁰,R¹¹, and R¹² are each a C₁₀-C₄₀ linear alkyl radical.
 8. The process ofclaim 1, wherein two or more of R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² areeach a C₁₀-C₂₂ linear alkyl radical.
 9. The process of claim 1, whereintwo or more of R¹, R², and R¹⁰ are each a C₁₀-C₄₀ linear alkyl and R⁸and R¹² are hydrogen.
 10. The process of claim 1, wherein two or more ofR¹, R², and R¹⁰ are each a C₁₀-C₂₂ linear alkyl and R⁸ and R¹² arehydrogen.
 11. The process of claim 1, wherein at least one of R⁸, R⁹,R¹⁰, R¹¹, and R¹² is a linear alkyl radical comprising 6 or more carbonatoms.
 12. The process of claim 1, wherein R⁸ and R¹² are hydrogen andR¹⁰ is a linear alkyl radical comprising 6 or more carbon atoms.
 13. Theprocess of claim 1, wherein R¹ is methyl and each of R² and R¹⁰ isC₆-C₄₀ linear alkyl radical.
 14. The process of claim 1, furthercomprising the step of filtering the mixture to remove the salt toproduce a clear homogeneous solution comprising the activator compoundaccording to formula (I) and optionally removing at least a portion ofthe solvent.
 15. The process of claim 1, wherein the period of time isless than or equal to about 24 hours.
 16. The process of claim 1,wherein the period of time is less than or equal to about 2 hours. 17.The process of claim 1, wherein a 5 millimole per liter mixture of theactivator compound in n-hexane, isohexane, cyclohexane,methylcyclohexane, or a combination thereof, forms a clear homogeneoussolution at 25° C.
 18. The process of claim 1, wherein a 10 millimoleper liter mixture of the activator compound in n-hexane, isohexane,cyclohexane, methylcyclohexane, or a combination thereof, forms a clearhomogeneous solution at 25° C.
 19. The process of claim 1, wherein a 20millimole per liter mixture of the activator compound in n-hexane,isohexane, cyclohexane, methylcyclohexane, or a combination thereof,forms a clear homogeneous solution at 25° C.
 20. The process of claim 1where aromatic solvents are absent.
 21. The process of claim 1, whereinthe solvent includes isohexane.
 22. The process of claim 1, wherein thesolvent includes n-hexane.
 23. A process of polymerizing olefins toproduce at least one polyolefin, the process comprising: i) contacting acompound according to formula (A) with a compound having the generalformula M-(BR⁴R⁵R⁶R⁷) in a solvent including isohexane, hexane, orn-hexane, or a combination thereof, at a reaction temperature rangingfrom 30° C. to 20° C. and for a period of time sufficient to produce amixture comprising an activator compound according to formula (I) and asalt having the formula M(X); wherein formula (A) is represented by:

wherein formula (I) is represented by:

wherein in each of formulae (A) and (I): each of R¹ and R² isindependently a hydrogen or a C₁-C₄₀ linear alkyl, with R⁸, R⁹, R¹⁰,R¹¹, and R¹² being independently C₁-C₄₀ linear alkyl and not hydrogen;R¹, R², R⁸, R⁹, R¹⁰, R¹¹, and R¹² together comprise 15 or more carbonatoms; each of R⁴, R⁵, R⁶, and R⁷ comprises an aromatic hydrocarbonhaving from 6 to 24 carbon atoms; at least one of R⁴, R⁵, R⁶, and R⁷ issubstituted with one or more fluorine atoms; X is halogen; and M is aGroup 1 metal; ii) filtering the mixture to remove the salt to produce aclear homogeneous solution comprising the activator compound accordingto formula (I) and optionally removing at least a portion of thesolvent; iii) combining the activator and a catalyst to form a catalystsystem, and iv) contacting at least one olefin with the catalyst systemand obtaining the polyolefin; wherein a 1 millimole per liter mixture ofthe activator compound in hexane, n-hexane, isohexane, or a combinationthereof, forms a clear homogeneous solution at 25° C.
 24. The process ofclaim 23, wherein the at least one olefin is propylene and thepolyolefin is isotactic polypropylene.
 25. The process of claim 23,wherein the at least one olefin is two or more different olefins. 26.The process of claim 23, wherein the at least one olefin is bothethylene and propylene.
 27. The process of claim 23, wherein the atleast one olefin comprises a diene.
 28. The process of claim 25 wherearomatic solvents are absent.
 29. The process of claim 23, wherein thesolvent includes isohexane.
 30. The process of claim 23, wherein thesolvent includes n-hexane.